CFS GAMESS-UK Molecular Electronic Structure System User Manual
Below you will find brief information for GAMESS-UK.This manual provides instructions for performing single-point SCF calculations, geometry optimizations, and transition state location. Includes details on force constant evaluations, graphical analysis, direct-SCF calculations, and CASSCF geometry optimizations.
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CONTENTS
Computing for Science (CFS) Ltd.,
CCLRC Daresbury Laboratory.
Generalised Atomic and Molecular Electronic Structure System
G A M E S S - U K
USER’S GUIDE and
REFERENCE MANUAL
Version 8.0
June 2008
PART 12. GAMESS-UK under UNIX
M.F. Guest, J. Kendrick, J.H. van Lenthe and P. Sherwood
Copyright (c) 1993-2008 Computing for Science Ltd.
This document may be freely reproduced provided that it is reproduced unaltered and in its entirety.
Contents
2 Single Point SCF Calculation
3 Sequence of Calculations on Water
4 SCF Calculations on Cubane, Nitrobenzene and Trinitrotoluene
6 Extended Basis Set Calculations of Na
11
13
16
6
9
2
4 i
CONTENTS 1
8 Graphical analysis of nickel tetracarbonyl
9 Two-Pair GVB Calculation on 1-imino-2,4-pentadiene
11 HCN/HNC Transition State Location
18
20
23
25
12 HSiP/HPSi Transition State Location
26
12.1 Numerical Force Constants
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
26
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
28
13 Use of Bond-centred Functions
14 SCF Analytic Force Constants for Ethylene
15 MP2 Analytic Force Constants for Ethylene
16 MP2 Polarisability for Ethylene
30
31
32
33
17 Direct-MP2 Calculation of Pyridine
18 CASSCF Geometry Optimisations
19 CASSCF + 2nd-order CI Calculations on BeO
20 MCSCF + 2nd-order CI Calculations on BeO
21 Table-CI calculations on the Ammonia Cation
22 ECP, CASSCF and Direct-CI Calculations on NiCCH
23 Table-CI Calculations of the Electronic Spectra of Pyridine
44
51
59
68
34
35
38
41
1 INTRODUCTION 2
1 Introduction
In the present section we consider initially execution of GAMESS–UK on a Linux workstation, although these notes are intended as a more general guide to running the code under the Unix operating system. Throughout this description we make the following assumptions:
• the user will in general submit jobs from a disk partition different to that where the direct access files used by GAMESS–UK will be cited: typically the latter will be striped. For the purpose of the present notes we assume that the various files involved will be routed to the partition /scr1/user, where the directory ’user’ has been created prior to job submission
(using the command mkdir), thus mkdir /scr1/user
• that all job inputs reside in the user’s home directory (or subdirectory thereof), and that all job output is to be routed back to that directory.
• We assume the user is submitting jobs directly to the background.
• In Part 13 we discuss execution of GAMESS–UK using the prepared script rungamess
• all of the commands in these notes belong to the C shell.
Note that all data input for the Unix implementation of GAMESS–UK may be presented in either upper or lower case. In the examples below we have used lower case input throughout.
Note that it is a trivial matter to convert data from under control of the dd command. Thus if upper case data input resides in the file upper, the following command dd if=upper of=lower conv=lcase will perform the necessary conversion to leave the required lower case input in the file lower.
Note that the executable for GAMESS–UK is assumed to reside in the file /scr1/wab/GAMESS-
UK/gamess. The following examples will be considered:
1. Single point SCF calculation of water using the default basis.
2. Sequence of calculations on water, including starting and restarting geometry optimisation of the neutral molecule, an RHF calculation on the
2
B
1 cation, boys localisation and 2-pair
GVB calculation of the neutral molecule.
3. Closed-shell SCF calculations on C
4
F
4
, C
6
H
5
NO
2 and C
6
H
2
(NO
2
)
3
CH
3
.
4. STO-3G calculation of Na
7
Mg
+
, together with an RHF and UHF calculation of the triplet state.
5. Extended basis set calculation on Na
7
Mg
+
, with SCF calculation of the singlet state preceding an RHF calculation of the triplet state.
1 INTRODUCTION 3
6. ECP calculation on Na
7
Mg
+ in a double-zeta valence basis, with SCF calculation of the singlet state preceding an RHF calculation of the triplet state.
7. 2-pair GVB calculation on 1-imino-2,4-pentadiene, CH
2
(CH)
4
NH
+
2
8. Graphical analysis of the X
1
A
1 state of Ni(CO)
4
.
9. STO-3G direct-SCF calculations on C
11
O
10
NPH
18
Be(C
5
H
5
)
2
.
and the geometry optimisation of
10. Determination of the transition state for the HCN/HNC isomerisation reaction. This example demonstrates usage of the three saddle point algorithms available, the default trust-region method plus the synchronous transit and Simons-Jorgensen algorithms.
11. Location of the transition state for the HPSi/HSiP isomerisation and subsequent force constant evaluation.
12. Specification of bond-centred functions, located at the midpoint of the C-N bond in the
HCN/HNC transition state.
13. SCF geometry optimisation and analytic force constants of C
2
H
4
.
14. MP2 geometry optimisation and analytic force constants of C
2
H
4
.
15. MP2 geometry optimisation and polarisability of C
2
H
4
.
16. Direct-MP2 calculation of C
5
H
5
N in a 6-31G* basis.
17. CASSCF geometry optimisation of the X
1
A
1 state of H
2
O.
18. CASSCF + 2nd-order CI calculations of the X
1
Σ
+ state of BeO.
19. MCSCF + 2nd-order CI calculations of the X
1
Σ
+ state of BeO.
20. Table-CI calculation of the X
2
A
1 and 1
2
A
1 states of the ammonia cation, NH
+
3 cation.
21. ECP calculation on NiCCH
2 state wavefunction.
with CASSCF and Direct-CI calculations of the lowest triplet
22. Table-CI calculations typical of those performed in the calculation of electronic spectra.
In this case we are studying the disposition of the lowest
1
A
1 and 1
1
A
2 states of pyridine.
The sequence of calculations involve the determination of the lowest 10 states of each category, performed in a DZ plus rydberg basis.
23. Full-CI calculations of the X
1
A
1 state of H
2
O.
2 SINGLE POINT SCF CALCULATION 4
2 Single Point SCF Calculation
Let us consider a simple SCF run for H
2
O in a 3-21G basis, and describe the various mechanisms available for running the job in terms of the citing of direct access files involved and the routing of job output. Note at the outset that GAMESS–UK reads from stdin and writes to stdout, so that both input and output may be controlled by the standard means.
• Let us assume that the following lines reside in the file myjob,
/scr1/wab/GAMESS-UK/bin/gamess << EOF title\h2o 3-21g scf zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end enter
EOF and are submitted to the background through the command myjob >& myjob.log &
This will result in the files used by GAMESS–UK, in this case ED2, ED3 and ED7 being created in the user’s own directory for the duration of the run, and deleted on job termination. The output from the job and any system diagnostics will be routed to the file myjob.log. Note that the user may assign execute attributes to the file myjob, using the chmod command, thus chmod 700 myjob
• Note that it is also possible to read the data from a separate file, so that myjob would comprise the single line
/scr1/wab/GAMESS-UK/bin/gamess < datain where datain contains just the GAMESS–UK data, thus title\h2o 3-21g scf zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end enter
In this case the job might equally well be submitted directly with the following command,
/scr1/wab/GAMESS-UK/bin/gamess < datain >& myjob.log &
• Now consider the changes to myjob required to route the direct access files from the user’s own directory to the disk partition /scr1, in particular to the directory /scr1/user.
Assuming this directory has been created by the user, thus
2 SINGLE POINT SCF CALCULATION 5 mkdir /scr1/user this may be achieved either by using the cd command at the outset of myjob, so as execute the job in the required directory, thus cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title\h2o 3-21g scf zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end enter
EOF in which case the direct access files will be deleted on job termination, or through the setenv command, thus
#!/bin/csh -f setenv ed2 /scr1/user/ed2 setenv ed3 /scr1/user/ed3 setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF title\h2o 3-21g scf zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end enter
EOF
In this case the files created in /scr1/user will not be deleted on job termination.
This provides, of course, the mechanism for keeping files between separate runs of the program, with the file names assigned though the setenv values. Thus to keep the mainfile and dumpfile with file names h2omain and h2odump would require the following job input:
#!/bin/csh -f setenv ed2 /scr1/user/h2omain setenv ed3 /scr1/user/h2odump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF title\h2o 3-21g scf zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end enter
EOF or, if using the cd command,
#!/bin/csh -f cd /scr1/user setenv ed2 h2omain setenv ed3 h2odump
3 SEQUENCE OF CALCULATIONS ON WATER 6
/scr1/wab/GAMESS-UK/bin/gamess << EOF title\h2o 3-21g scf zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end enter
EOF with the scratchfile (ed7) omitted from the setenv commands.
Alternatively, instead of setting the names of the files through the setenv command, it is possible to use ”file” pre-directives within the body of the GAMESS-UK input. Thus the following:
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title\h2o 3-21g scf file ed2 h2omain file ed3 h2odump zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end enter
EOF achieves the same as using the setenv command. For all the following examples, either setenv commands run in the shell, or file directives in the GAMESS-UK input can be used interchangably.
3 Sequence of Calculations on Water
In this example we include a sequence of job files for performing various calculations based on the H
2
O example given above.
1. This run utilises the vectors made above. Both bond length and bond angle are to be optimised.
#!/bin/csh -f setenv ed2 /scr1/user/h2omain setenv ed3 /scr1/user/h2odump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title water optimisation at scf level 3-21g basis set zmat angstrom o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
3 SEQUENCE OF CALCULATIONS ON WATER 7 end runtype optimise enter
EOF
2. This example would be used to complete, if necessary, the run started in 1.
#!/bin/csh -f setenv ed2 /scr1/user/h2omain setenv ed3 /scr1/user/h2odump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart optimise title water optimisation at scf level 3-21g basis set zmat angstrom o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end runtype optimise enter
EOF
3. This example performs an open-shell RHF calculation at the optimised geometry from 2.
(note the RESTART usage).
#!/bin/csh -f setenv ed2 /scr1/user/h2omain setenv ed3 /scr1/user/h2odump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title h2o+ doublet b1 state - ground state geometry charge 1 mult 2 zmat angs o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end enter
EOF
4. The valence shell scf mos are to be localised. For the purpose of the example below it is assumed that orbitals 2 and 3 are the bond orbitals. The CHARGE and MULT directives are required to override the values set in the preceding job on the doublet cation.
3 SEQUENCE OF CALCULATIONS ON WATER 8
#!/bin/csh -f setenv ed2 /scr1/user/h2omain setenv ed3 /scr1/user/h2odump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title lmos for h2o-ground state geometry charge 0 mult 1 zmat angs o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end runtype analyse local
2 to 5 end vectors 1 enter 5
EOF
5. The localised orbitals are restored from section 5 and the NOGEN facility used to generate the virtual pairs of the two bond orbitals. The SWAP directive has been used to move the localised bond orbitals to the top of the occupied orbital list. The NOGEN facility reorders the orbitals so that the GVB pairs occur together. Note the ADAPT OFF specification, now required when using localised orbitals as the input orbital set.
#!/bin/csh -f setenv ed2 /scr1/user/h2omain setenv ed3 /scr1/user/h2odump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title water gvb calculation using localised orbitals adapt off zmat ang o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end scftype gvb 2 vectors nogen 5 swap
2 5
3 4
4 SCF CALCULATIONS ON CUBANE, NITROBENZENE AND TRINITROTOLUENE9 end enter
EOF
4 SCF Calculations on Cubane, Nitrobenzene and Trinitrotoluene
We show below the job files for three straightforward closed-shell SCF calculations, providing more examples of z-matrix specification and reliance on the default options in such calculations.
In each case the direct access files will be deleted on job completion.
Closed shell SCF Job for C
4
F
4
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title
**** c4f4 3/21g **** zmat angs x c 1 r1 c 1 r2 2 90.
c 1 r1 3 90.
2 180.
c 1 r2 4 90.
3 180.
x 2 1.
1 90.
f 2 r3 6 90.
x 4 1.
1 90.
f 4 r3 8 90.
x 3 1.
1 90.
3 0.
3 180.
3 0.
3 180.
4 0.
f 3 r3 10 90.
4 180.
x 5 1.
1 90.
4 0.
f 5 r3 12 90.
4 180.
variables r1 1.2
r2 1.3
r3 1.313
end enter
EOF
Closed shell SCF Job for C
6
H
5
NO
2
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title c6h5.no2
3-21g accuracy 20 7 noprint zmat angstrom c
4 SCF CALCULATIONS ON CUBANE, NITROBENZENE AND TRINITROTOLUENE10 rcc1 1.37
rcc2 1.43
rcc3 1.37
rno1 1.21
rch1 1.084
rch2 1.084
rch3 1.084
t1 120.0
t2 120.0
t3 120.0
t5 120.0
t6 120.0
t7 120.0
t8 120.0
p1 90.0
p2 180.0
p3 0.0
p5 0.0
p6 0.0
p7 0.0
end maxcyc 20 enter
EOF n 1 rcn x 2 1.0 1 90.0
c 1 rcc1 2 t1 3 p1 c 1 rcc1 2 t1 3 -p1 c 4 rcc2 1 t2 2 p2 c 5 rcc2 1 t2 2 p2 c 7 rcc3 5 t3 1 p3 o 2 rno1 1 t5 3 -90.0
o 2 rno1 1 t5 3 90.0
h 4 rch1 1 t6 2 p5 h 5 rch1 1 t6 2 p5 h 6 rch2 4 t7 11 p6 h 7 rch2 5 t7 12 p6 h 8 rch3 7 t8 14 p7 variables rcn 1.49
Closed shell SCF Job for C
6
H
2
(NO
2
)
3
CH
3 c c c c
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title
2,4,6 tri-nitro-toluene. 3-21g basis.
noprint distance basis vectors hessian zmat angstrom x
1
1
1
1 r1 r2 r2 r3
2
2
2 a1 a1 a2
3
3
180.
0.
5 STO-3G CALCULATIONS ON NA
7
MG
+
11 c n c x o o n 4 o 12 o 12
9
9
1
3
1
1 r3
1.
r4 r5 r6 r7 r5 r6 r7 x n o 16 o 16
8
8
1.
r8 r9 r9
1
15 x c
2 1.
h 20 r11
1
2 r10 19
2
8
8
2
4
4
3
3
7
2
2
2 a4 a5 a3 a4 a5 a2 3
90.
3
90.
2 a3 1
1
2
2
2
2
90.
6
90.
1 a6 a6
5
5
90.
4
90.
1 a7 19
180.
180.
180.
180.
0.
180.
180.
0.
180.
0.
180.
0.
180.
0.
180.
90.
h h h 20 r12 h 20 r12
5
6 r13 r13
8
8
2
2 a8 21 120.
a8 21 -120.
a9 a9
6
5
180.
180.
variables r1 1.431\r2 1.367\r3 1.397\r4 1.395
a1 60.38\a2 120.67
r5 1.521\r8 1.505\r6 1.277\r7 1.278\r9 1.277
a3 123.52\a4 121.19\a5 116.17\a6 117.53
r10 1.529\r11 1.087\r12 1.082
a7 110.07\a8 109.7
r13 1.086\a9 121.26
end enter
EOF
5 STO-3G Calculations on Na
7
Mg
+
In this calculation we perform an STO-3G calculation on Na
7
Mg
+
, followed by an RHF and then
UHF calculation on the triplet state. Note the use of the SUPER directive to ensure an integral file format compatible with the use of BYPASS in the subsequent RHF and UHF calculations.
Closed shell SCF Job
#!/bin/csh -f setenv ed2 /scr1/user/namgmain setenv ed3 /scr1/user/namgdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF title
* na7mg+ * sto-3g * closed shell * scf-energy= -1314.828516
mult 1 super force charge 1 zmat angs mg
5 STO-3G CALCULATIONS ON NA
7
MG
+ na 1 r1 na 1 r2 2 90.
na 1 r2 2 90. 3 72.
na 1 r2 2 90. 4 72.
na 1 r2 2 90. 5 72.
na 1 r2 2 90. 6 72.
na 1 r1 3 90. 2 180.
variables r1 3.0286740
r2 3.194799
end basis sto3g level 1.5
10 1.0
maxcyc 40 enter
EOF
Open shell RHF Job
#!/bin/csh -f setenv ed2 /scr1/user/namgmain setenv ed3 /scr1/user/namgdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title
* na7mg+ * sto-3g * triplet * scf energy=-1314.900851
super force bypass mult 3 charge 1 zmat angs mg na 1 r1 na 1 r2 2 90.
na 1 r2 2 90. 3 72.
na 1 r2 2 90. 4 72.
na 1 r2 2 90. 5 72.
na 1 r2 2 90. 6 72.
na 1 r1 3 90. 2 180.
variables r1 3.0286740
r2 3.194799
end basis sto3g maxcyc 40 enter
EOF
UHF Job
#!/bin/csh -f setenv ed2 /scr1/user/namgmain setenv ed3 /scr1/user/namgdump setenv ed7 /scr1/user/ed7
12
6 EXTENDED BASIS SET CALCULATIONS OF NA
7
MG
+
13
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart super force title
* na7mg+ * sto-3g * triplet * uhf energy=-1314.901919
mult 3 charge 1 bypass zmat angs mg na 1 r1 na 1 r2 2 90.
na 1 r2 2 90. 3 72.
na 1 r2 2 90. 4 72.
na 1 r2 2 90. 5 72.
na 1 r2 2 90. 6 72.
na 1 r1 3 90. 2 180.
variables r1 3.0286740
r2 3.194799
end basis sto3g scftype uhf vectors 5 enter
EOF
Note that we are using the energy ordered open-shell RHF eigenvectors to initiate the UHF calculation (as written to the default section 5 by the Open shell RHF Job). Had this section not been specified using the VECTORS directive, then the closed-shell SCF MOs would been used in default.
6 Extended Basis Set Calculations of Na
7
Mg
+
In this example we use the STO-3G calculation on Na
7
Mg
+
, performed above as a starting point for a more extensive basis set calculation. In particular the set of closed-shell vectors is restored under control of GETQ, with the STO-3G Dumpfile used as a ‘foreign’ Dumpfile.
We then perform an RHF calculation on the open-shell singlet state of Na
7
Mg
+
, using the integrals calculated in the closed-shell case. Note that the OPEN directive is now required for this low-spin state.
Closed shell SCF Job
#!/bin/csh -f setenv ed2 /scr1/user/namgmain setenv ed3 /scr1/user/namgdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF dumpfile ed3 500 title
6 EXTENDED BASIS SET CALCULATIONS OF NA
7
MG
+
* na7mg+ (4s3p//4s3p1d) scf energy=-1330.808742
mult 1 charge 1 super off noprint vectors zmat angs mg na 1 r1 na 1 r2 2 90.
na 1 r2 2 90. 3 72.
na 1 r2 2 90. 4 72.
na 1 r2 2 90. 5 72.
na 1 r2 2 90. 6 72.
na 1 r1 3 90. 2 180.
variables r1 3.0286740
r2 3.194799
end basis s mg
.005004
5609.67
.037083
841.969
.171495
191.263
.444597
53.2621
.480060
16.6003
s mg
.352170
2.97082
.692921
1.00728
s mg
1.00000
.113641
s mg
1.000000
.044678
p mg
.039884
50.9665
.223321
11.4364
.514536
3.21935
p mg
1.00000
0.914433
p mg
1.00000
0.16
d mg
1.00000
0.175
s na
.003064
6902.67
.022198
1059.04
.095576
255.445
.280448
77.3172
.452587 26.8224
s na
.29313
10.0718
s na
1.000000
2.17902
s na
1.000000 .689482
1.0
.040274
14
6 EXTENDED BASIS SET CALCULATIONS OF NA
7
MG
+ p na
.042422
38.9438
.229433
8.71012
.509774
2.42053
p na
1.00000
.661896
p na
1.0
end
.065
maxcyc 40 vectors getq ed3 1 1 enter
EOF
Open shell RHF Job
#!/bin/csh -f setenv ed2 /scr1/user/namgmain setenv ed3 /scr1/user/namgdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF dumpfile ed3 500 restart
# open shell scf using closed shell vectors from above *
# bypass integral evaluation * title
* na7mg+ (4s3p//4s3p1d) triplet rhf * energy=-1330.766950
super off bypass mult 1 charge 1 zmat angs mg na 1 r1 na 1 r2 2 90.
na 1 r2 2 90. 3 72.
na 1 r2 2 90. 4 72.
na 1 r2 2 90. 5 72.
na 1 r2 2 90. 6 72.
na 1 r1 3 90. 2 180.
variables r1 3.0286740
r2 3.194799
end basis s mg
.005004
5609.67
.037083
841.969
.171495
191.263
.444597
53.2621
.480060
16.6003
s mg
.352170
2.97082
.692921
1.00728
s mg
15
7 ECP CALCULATIONS OF NA
7
MG
+
16
1.00000
.113641
s mg
1.000000
.044678
p mg
.039884
50.9665
.223321
11.4364
.514536
3.21935
p mg
1.00000
0.914433
p mg
1.00000
0.16
d mg
1.00000
0.175
s na
.003064
6902.67
.022198
1059.04
.095576
255.445
.280448
77.3172
.452587 26.8224
.29313
10.0718
s na
1.000000
2.17902
s na
1.000000 .689482
s na
1.0
p na
.040274
.042422
38.9438
.229433
8.71012
.509774
2.42053
p na
1.00000
.661896
p na
1.0
.065
end open 1 1 1 1 maxcyc 40 enter
EOF
7 ECP calculations of Na
7
Mg
+
In this example on Na
7
Mg
+
, we perform a local ECP calculation, using the Hay-Wadt ECP’s, together with the associated double zeta basis sets, augmented by a d-function on Mg. Having carried out the closed-shell SCF calculation, we perform an RHF calculation on the singlet state of Na
7
Mg
+
, using the integrals calculated in the closed-shell case. Note that we are re-using the files from the previous example.
Closed shell SCF Job
#!/bin/csh -f
7 ECP CALCULATIONS OF NA
7
MG
+ setenv ed2 /scr1/user/namgmain setenv ed3 /scr1/user/namgdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF title na7mg+ ecp LANL ecp /closed shell singlet charge 1 super off zmat angs mg na 1 r1 na 1 r2 2 90.
na 1 r2 2 90. 3 72.
na 1 r2 2 90. 4 72.
na 1 r2 2 90. 5 72.
na 1 r2 2 90. 6 72.
na 1 r1 3 90. 2 180.
variables r1 3.0286740
r2 3.194799
end basis ecpdz na ecpdz mg d mg
1.0 0.175
end ecp na na mg mg level 1.0
enter
EOF
Open shell RHF Job
#!/bin/csh -f setenv ed2 /scr1/user/namgmain setenv ed3 /scr1/user/namgdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title na7mg+ ecp /open-shell singlet rhf mult 1 charge 1 super off bypass zmat angs mg na 1 r1 na 1 r2 2 90.
na 1 r2 2 90. 3 72.
na 1 r2 2 90. 4 72.
na 1 r2 2 90. 5 72.
17
8 GRAPHICAL ANALYSIS OF NICKEL TETRACARBONYL na 1 r2 2 90. 6 72.
na 1 r1 3 90. 2 180.
variables r1 3.0286740
r2 3.194799
end basis ecpdz na ecpdz mg d mg
1.0 0.175
end ecp na na mg mg runtype scf open 1 1 1 1 level 0.3 1.0
enter
EOF
18
8 Graphical analysis of nickel tetracarbonyl
The following example illustrates features of the Graphical Analysis module, in analysing the ground state SCF wavefunction of Ni(CO)
4
. Let us assume the following job has been used in constructing this wavefunction.
#!/bin/csh -f setenv ed2 /scr1/user/nicomain setenv ed3 /scr1/user/nicodump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF title\ni(co)4 .. 3-21g / SCF total energy -1947.868687
zmat angstrom ni c 1 nic c 1 nic 2 109.471
c 1 nic 2 109.471 3 120.0
c 1 nic 2 109.471 4 120.0
x 2 1.0 1 90.0 3 180.0
o 2 co 6 90.0 1 180.0
x 3 1.0 1 90.0 2 180.0
o 3 co 8 90.0 1 180.0
x 4 1.0 1 90.0 5 180.0
o 4 co 10 90.0 1 180.0
x 5 1.0 1 90.0 4 180.0
o 5 co 12 90.0 1 180.0
variables nic 1.831
co 1.131
end level 1.5
8 GRAPHICAL ANALYSIS OF NICKEL TETRACARBONYL 19 enter
EOF
Examination of the output reveals the following symmetry designation:
******************
MOLECULAR SYMMETRY
******************
MOLECULAR POINT GROUP TD
ORDER OF PRINCIPAL AXIS 0
SYMMETRY POINTS :
POINT 1 :
POINT 2 :
POINT 3 :
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
1.0000000
0.0000000
1.0000000
0.0000000
and the following atomic coordinates:
0.0000000
-1.9976836
1.9976836
-1.9976836
1.9976836
-3.2316433
3.2316433
-3.2316433
3.2316433
0.0000000
1.9976836
-1.9976836
-1.9976836
1.9976836
3.2316433
-3.2316433
-3.2316433
3.2316433
0.0000000
-1.9976836
-1.9976836
1.9976836
1.9976836
-3.2316433
-3.2316433
3.2316433
3.2316433
O
O
O
C
O
C
C
NI
C
The following job may be used to construct a total density plot of the SCF wavefunction in a plane containing the Ni atom and two carbonyl groups, with the Ni at the centre of the plot: a contour plot will be generated on line printer output.
#!/bin/csh -f setenv ed2 /scr1/user/nicomain setenv ed3 /scr1/user/nicodump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title\ni(co)4 .. 3-21g / SCF total energy -1947.868687
zmat angstrom ni c 1 nic c 1 nic 2 109.471
c 1 nic 2 109.471 3 120.0
c 1 nic 2 109.471 4 120.0
x 2 1.0 1 90.0 3 180.0
o 2 co 6 90.0 1 180.0
x 3 1.0 1 90.0 2 180.0
o 3 co 8 90.0 1 180.0
x 4 1.0 1 90.0 5 180.0
o 4 co 10 90.0 1 180.0
9 TWO-PAIR GVB CALCULATION ON 1-IMINO-2,4-PENTADIENE x 5 1.0 1 90.0 4 180.0
o 5 co 12 90.0 1 180.0
variables nic 1.831
co 1.131
end runtype analyse graphics gdef type 2d title square 2d grid ni(co)4 - total density calc type dens title ni(co)4 - total density section 151 plot type line title ni(co)4 - total density vectors 1 enter
EOF
9 Two-Pair GVB Calculation on 1-imino-2,4-pentadiene
Closed shell SCF Job
#!/bin/csh -f setenv ed2 /scr1/user/gvbmain setenv ed3 /scr1/user/gvbdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF
# open shell rhf sto3g
# check super force title
1-imino-2,4-pentadiene * energy=-245.073477
super force nosym mult 1 accuracy 20 7 charge 1 zmat angs c c 1 r1 c 2 r2 1 a1 c 3 r3 2 a2 1 cx c 4 r4 3 a3 2 c2 n 1 r5 2 a4 3 c2 h 1 r6 2 a5 3 c1 h 2 r7 3 a6 7 c2 h 3 r8 4 a7 8 c2 h 4 r9 5 a8 9 c2
*
*
20
9 TWO-PAIR GVB CALCULATION ON 1-IMINO-2,4-PENTADIENE r5 r6 r7 r8 r9 r10 r11 h 5 r10 4 a9 10 c1 h 5 r11 4 a10 11 c2 h 6 r12 1 a11 7 c1 h 6 r13 1 a12 13 c2 variables r1 1.3463261
r2 r3 r4
1.4632685
1.3961480
1.3568062
1.3416773
1.0748794
1.0669518
1.0811641
1.0707072
1.0729928
1.0747118
r12 r13
0.9971261
0.9985437
a1 118.2539432
a2 122.8419092
a3 119.3229511
a4 125.9857684
a5 119.9766875
a6 122.1120978
a7 116.3317717
a8 120.9014063
a9 121.5606571
a10 121.8124933
a11 120.9303349
a12 121.8324395
constants c1 0.
c2 180.
cx 90.
end basis sto3g scftype rhf open 1 1 1 1 enter
EOF
Two-Pair GVB Job
#!/bin/csh -f setenv ed2 /scr1/user/gvbmain setenv ed3 /scr1/user/gvbdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF
# gvb-scf with two pairs
# bypass integral evaluation restart bypass title
1-imino-2,4-pentadiene * energy=-245.1146628
mult 1
*
*
21
9 TWO-PAIR GVB CALCULATION ON 1-IMINO-2,4-PENTADIENE accuracy 20 7 super force nosym charge 1 zmat angs c c 1 r1 c 2 r2 1 a1 c 3 r3 2 a2 1 cx c 4 r4 3 a3 2 c2 n 1 r5 2 a4 3 c2 h 1 r6 2 a5 3 c1 h 2 r7 3 a6 7 c2 h 3 r8 4 a7 8 c2 h 4 r9 5 a8 9 c2 h 5 r10 4 a9 10 c1 h 5 r11 4 a10 11 c2 r7 r8 r9 r10 r11 r12 r13 r2 r3 r4 r5 r6 h 6 r12 1 a11 7 c1 h 6 r13 1 a12 13 c2 variables r1 1.3463261
1.4632685
1.3961480
1.3568062
1.3416773
1.0748794
1.0669518
1.0811641
1.0707072
1.0729928
1.0747118
0.9971261
0.9985437
a1 118.2539432
a2 122.8419092
a3 119.3229511
a4 125.9857684
a5 119.9766875
a6 122.1120978
a7 116.3317717
a8 120.9014063
a9 121.5606571
a10 121.8124933
a11 120.9303349
a12 121.8324395
constants c1 0.
c2 180.
cx 90.
end basis sto3g runtype scf scftype gvb 2 enter
EOF
22
10 DIRECT-SCF CALCULATIONS 23
10 Direct-SCF Calculations
In the first example below we show a direct-SCF calculation in which the input geometry in cartesian coordinates is converted to z–matrix representation; the second calculation features geometry optimisation of Be(C
5
H
5
)
2 using the direct-SCF module.
#!/bin/csh -f setenv ed3 /scr1/user/dscfdump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF
# direct scf generate zmatrix sto3g-basis title
* test2a * energy=-1550.28679356
charge -2 geometry distance angles torsions
-2.9512196
-0.1547624
-2.3287565
-1.0815728
-1.1603816
3.5011251
2.9474874
1.7359097
1.3150929
4.1957289
-1.9700376
-3.5363478
1.6367703
-0.8475562
2.1566895
-0.4797763
-2.6669663
-3.6433853
1.7242063
1.4125382
2.9182102
-1.5385361
-2.8467927
-1.5624978
-3.4976155
-0.4827273
1.0782554
-0.1090391
1.8702785
-0.4054688
all
8.0
6.0
1.0
6.0
1.0
7.0
1.0
6.0
1.0
8.0
-0.3417469
0.0532604
-0.3292201
-1.4442971
-2.9721287
-3.3279629
-5.1750163
3.5022051
3.8272799
5.9011224
7.1126500
2.1997957
1.8049798
3.9122805
-1.1895255
-3.1681491
0.0783133
-0.6802213
-0.9534701
1.0197182
-1.8751357
6.0
1.0
8.0
1.0
6.0
1.0
6.0
-4.8159917
-6.8815215
-5.4889849
-7.5612331
-7.4278090
5.7357642
5.5713092
7.8017770
7.0224823
4.4971112
2.7942026
6.1460386
6.0739323
4.3945431
3.1285958
1.7094915
5.1679189
6.8328410
-3.8035825
-1.8646838
-0.3379417
1.4363625
2.5896385
1.6502323
3.4875662
1.7463198
2.6479587
1.0
1.0
8.0
6.0
1.0
6.0
8.0
6.0
1.0
8.3530583
5.6784964
5.9321304
-2.9668945
6.7897779
-1.7121829
7.7021385
-4.8380024
7.1302965
-6.7576698
7.6050313
-4.5640081
-1.5715523
-2.9124352
-3.9184431
-4.8124121
-3.1659952
-7.1913356
-6.0342521
-3.6456571
-4.4900093
-5.1460285
9.4719556
-4.5440252
9.3293820
4.5891096
-0.1498644
-1.2970693
-3.0617741
0.0564767
-0.3499893
2.0812894
0.9658559
0.9101853
15.0
-0.3438675
8.0
-0.4943459
3.8664887
8.0
8.0
-0.5381892
2.6957586
1.0
1.0
1.0
6.0
8.0
6.0
1.0
1.0
8.0
o h c h c h c n h c h c h o o c h o c h h c o c h h o o p o h h o c h c h h o
*
10 DIRECT-SCF CALCULATIONS
-9.1872029
-7.5522104
end basis sto3g scftype direct enter
EOF
6.0381561
7.5798978
0.4734880
2.5757500
1.0
1.0
h h
Direct-SCF Geometry Optimisation of Be(C
5
H
5
)
2
#!/bin/csh -f
/scr1/wab/GAMESS-UK/bin/gamess << EOF title be(c5h5)2 sto3g optimised total energy = -394.2789851 au zmatrix angstrom x x 1 fxa c 2 xc 1 xxc c 2 xc 1 xxc 3 cxc c 2 xc 1 xxc 4 cxc c 2 xc 1 xxc 3 -cxc c 2 xc 1 xxc 6 -cxc x 2 xx 3 xxc 4 -xxc h 2 hx 8 hxx 3 hcx h 2 hx 8 hxx 4 hcx h 2 hx 8 hxx 5 hcx h 2 hx 8 hxx 6 hcx h 2 hx 8 hxx 7 hcx x 2 fxt 3 xxc 4 xxc c 14 xc 1 xxc 3 cxxc c 14 xc 1 xxc 15 cxc c 14 xc 1 xxc 16 cxc c 14 xc 1 xxc 15 -cxc c 14 xc 1 xxc 18 -cxc x 14 xx 15 xxc 16 -xxc h 14 hx 20 hxx 15 hcx h 14 hx 20 hxx 16 hcx h 14 hx 20 hxx 17 hcx h 14 hx 20 hxx 18 hcx h 14 hx 20 hxx 19 hcx be 2 fxa 3 xxc 4 xxc variables fxa 1.47
fxt 3.37
xc 1.22
hx 2.12
hxx 88.4
constants cxc 72.0
cxxc 36.0
xxc 90.0
hcx 0.0
xx end
1.0
basis sto3g
24
11 HCN/HNC TRANSITION STATE LOCATION 25 runtype optimize scftype direct level 2.0 10 1.4
enter
EOF
11 HCN/HNC Transition State Location
Transition state calculation for the HCN,HNC isomerisation process. The first job uses the default trust region algorithm, the second the synchronous transit algorithm, and the third the
Jorgensen-Simons algorithm.
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title hcn 4-31G saddle point zmat angs c x 1 1.0
n 1 cn 2 90.0
h 1 ch 2 90.0 3 hcn variables cn 1.1484 type 3 ch 1.5960 type 3 hcn 90.0 type 3 end basis 4-31g runtype saddle enter
EOF
Saddle point for HCN using the synchronous transit algorithm - note the definition of the minima required (on the variable definition lines) and the LSEARCH directive. The default saddle point method does nor require minima definition (see above)
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title hcn saddle point - synchronous transit zmat angs c x 1 1.0
n 1 cn 2 90.0
h 1 ch 2 90.0 3 hcn variables cn 1.1484 minima 1.1371 1.1597
ch 1.5960 minima 1.0502 2.1429
hcn 90.0
minima 180.0
0.0
end
12 HSIP/HPSI TRANSITION STATE LOCATION basis 4-31g runtype saddle lsearch 0 4 enter
EOF
Saddle point for HCN using the Jorgensen-Simons algorithm.
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title hcn/hnc ts search . jorgensen-simons zmat angs c x 1 1.0
n 1 cn 2 90.0
h 1 ch 2 90.0 3 hcn variables cn 1.1484 type 3 ch 1.5960 type 3 hcn 90.0
type 3 end basis 4-31g runtype saddle jorgensen powell maxjor 55 recalc off rfo off cutoffs optprint on xtol 0.0018
enter
EOF
26
12 HSiP/HPSi Transition State Location
This example is concerned with locating the transition state in the HPSi, HSiP isomerisation process, and calculating the associated vibrational frequencies. We provide sample jobs using both numerical and analytical techniques in the transition state location and subsequent force constant evaluation. Note that the latter example is computationally the most efficient, and should certainly be adopted for small–medium sized molecules.
12.1
Numerical Force Constants
In the first step we perform an initial SCF for subsequent use in the saddle point calculation.
Closed shell SCF Job
#!/bin/csh -f
12 HSIP/HPSI TRANSITION STATE LOCATION 27 setenv ed2 /scr1/user/hpsimain setenv ed3 /scr1/user/hpsidump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF title psih saddle point zmat ang p x 1 1.0
si 1 psi 2 90.0
h 1 ph 2 90.0 3 hpsi variables psi 2.053 type 3 ph 2.44
type 3 hpsi 51.02 type 3 end enter
EOF
In the subsequent location of the transition state, note the use of TYPE 3 which causes the program to calculate the complete force constant matrix numerically before commencing the search for the saddle point, and the use of XTOL to provide more stringent optimisation criteria in view of the subsequent force constant evaluation. LOCK is used to retain the initial SCF configuration throughout the search.
Transition State Job
#!/bin/csh -f setenv ed2 /scr1/user/hpsimain setenv ed3 /scr1/user/hpsidump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new bypass title psih <-> hpsi saddle point zmat angs p x 1 1.0
si 1 psi 2 90.0
h 1 ph 2 90.0 3 hpsi variables psi 2.053 type 3 ph 2.44
type 3 hpsi 51.02 type 3 end runtype saddle lock xtol 0.0005
enter 2
EOF
Finally we present the job for numerical evaluation of the force constants at the optimised geometry. Note the use of restart in requesting usage of the geometry from the Dumpfile, rather
12 HSIP/HPSI TRANSITION STATE LOCATION 28 than from the data file.
Numerical Force Constant Job
#!/bin/csh -f setenv ed2 /scr1/user/hpsimain setenv ed3 /scr1/user/hpsidump setenv ed7 /scr1/user/ed7
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title psih <-> hpsi saddle point numerical fcm zmat angs p x 1 1.0
si 1 psi 2 90.0
h 1 ph 2 90.0 3 hpsi variables psi 2.053 type 3 ph 2.44
type 3 hpsi 51.02 type 3 end runtype force vectors 2 lock enter 3
EOF
12.2
Analytic Force Constants
In the first step we perform the computation of the trial hessian under RUNTYPE HESSIAN control for subsequent use in the saddle point calculation.
Computing the trial Hessian
#!/bin/csh -f cd /scr1/user setenv ed2 hpsimain setenv ed3 hpsidump
/scr1/wab/GAMESS-UK/bin/gamess << EOF title psih trial hessian / SCF zmat ang p x 1 1.0
si 1 psi 2 90.0
h 1 ph 2 90.0 3 hpsi variables psi 2.053
ph 2.44
hpsi 51.02
end
12 HSIP/HPSI TRANSITION STATE LOCATION 29 runtype hessian enter
EOF
In the subsequent location of the transition state, note the use of the FCM keyword on the
RUNTYPE data line to restore the trial hessian computed in the first job and the use of XTOL to provide more stringent optimisation criteria in view of the subsequent force constant evaluation. LOCK is used to retain the initial SCF configuration throughout the search.
Transition State Job
#!/bin/csh -f cd /scr1/user setenv ed2 hpsimain setenv ed3 hpsidump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title psih <-> hpsi saddle point location / using trial hessian zmat angs p x 1 1.0
si 1 psi 2 90.0
h 1 ph 2 90.0 3 hpsi variables psi 2.053
ph 2.44
hpsi 51.02
end runtype saddle fcm xtol 0.0005
vectors 1 lock enter 2
EOF
Finally we present the job for analytic computation of the force constants at the optimised geometry under control of runtype hessian. Note the use of restart in requesting usage of the geometry from the Dumpfile, rather than from the data file.
Analytic Force Constant Job
#!/bin/csh -f cd /scr1/user setenv ed2 hpsimain setenv ed3 hpsidump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title psih <-> hpsi saddle point / force constants zmat angs p
13 USE OF BOND-CENTRED FUNCTIONS x 1 1.0
si 1 psi 2 90.0
h 1 ph 2 90.0 3 hpsi variables psi 2.053
ph 2.44
hpsi 51.02
end runtype hessian vectors 2 lock enter 2
EOF
30
13 Use of Bond-centred Functions
In this example we demonstrate the use of bond-centred functions (s,p), cited at the mid-point of the C-N bond in the HCN, HNC transition state.
#!/bin/csh -f cd /scr1/user
/scr1/wab/GAMESS-UK/bin/gamess << EOF title hcn-hnc basis - dunning (9s5p-3s2p) bond(s,p) + p(h) zmat angstrom c bq 1 rcn2 x 2 1.0 1 90.0
n 2 rcn2 3 90.0 1 180.0
x 1 1.0 2 90.0 3 0.0
h 1 rch 5 90.0 4 phi variables rcn2 0.5991
rch 1.2128
phi 71.2
end basis sv h p h
1.0 0.7
s bq
1.0 1.0
p bq
1.0 0.7
sv c sv n end enter
EOF
14 SCF ANALYTIC FORCE CONSTANTS FOR ETHYLENE 31
14 SCF Analytic Force Constants for Ethylene
We consider below computing the analytic force constants for C
2
H
4
, initially optimising the molecule at the SCF level, followed by the force constant calculation. Note the use of the
XTOL directive in the optimisation job to ensure a higher degree of optimisation than that derived using the default XTOL.
Geometry Optimisation
#!/bin/csh -f cd /scr1/user setenv ed2 c2h4main setenv ed3 c2h4dump
/scr1/wab/GAMESS-UK/bin/gamess << EOF title ethylene 6-31g** geometry optimisation zmatrix angstrom c c 1 cc h 1 ch 2 hcc h 1 ch 2 hcc 3 180.0
h 2 ch 1 hcc 3 0.0
h 2 ch 1 hcc 3 180.0
variables cc 1.40
ch 1.10
hcc 118.0
end basis 6-31g** runtype optimize xtol 0.0001
enter
EOF
Analytic Force Constants
#!/bin/csh -f cd /scr1/user setenv ed2 c2h4main setenv ed3 c2h4dump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title ethylene 6-31g** ground state vibrational frequencies zmatrix angstrom c c 1 cc h 1 ch 2 hcc h 1 ch 2 hcc 3 180.0
h 2 ch 1 hcc 3 0.0
h 2 ch 1 hcc 3 180.0
variables cc 1.40
15 MP2 ANALYTIC FORCE CONSTANTS FOR ETHYLENE 32 ch 1.10
hcc 118.0
end basis 6-31g** runtype hessian enter
EOF
15 MP2 Analytic Force Constants for Ethylene
We consider below computing the analytic force constants for C
2
H
4
, initially optimising the molecule at the MP2 level, followed by the force constant calculation. Note again the use of the XTOL directive in the optimisation job to ensure a higher degree of optimisation than that derived using the default XTOL.
MP2 Geometry Optimisation
#!/bin/csh -f cd /scr1/user setenv ed2 c2h4main setenv ed3 c2h4dump
/scr1/wab/GAMESS-UK/bin/gamess << EOF title ethylene 6-31g** MP2/ optimised total energy = -78.3272309
zmatrix angstrom c c 1 cc h 1 ch 2 hcc h 1 ch 2 hcc 3 180.0
h 2 ch 1 hcc 3 0.0
h 2 ch 1 hcc 3 180.0
variables cc 1.40
ch 1.10
hcc 118.0
end basis 6-31g** runtype optimize scftype mp2 xtol 0.0001
enter
EOF
MP2 Analytic Force Constants
#!/bin/csh -f cd /scr1/user setenv ed2 c2h4main setenv ed3 c2h4dump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart
16 MP2 POLARISABILITY FOR ETHYLENE 33 title ethylene MP2/6-31g** ground state vibrational frequencies
#freq 847.7, 941.6, 994.1, 1091.6, 1267.4, 1414.5,
#freq 1525.2, 1729.7, 3241.3, 3259.2, 3336.6, 3359.8
zmatrix angstrom c c 1 cc h 1 ch 2 hcc h 1 ch 2 hcc 3 180.0
h 2 ch 1 hcc 3 0.0
h 2 ch 1 hcc 3 180.0
variables cc 1.40
ch 1.10
hcc 118.0
end basis 6-31g** runtype hessian scftype mp2 enter
EOF
16 MP2 Polarisability for Ethylene
We consider below computing the molecular polarisability of C
2
H
4
, initially optimising the molecule at the MP2 level, followed by the property calculation. Note again the use of the
XTOL directive in the optimisation job to ensure a higher degree of optimisation than that derived using the default XTOL.
MP2 Geometry Optimisation
#!/bin/csh -f cd /scr1/user setenv ed2 c2h4main setenv ed3 c2h4dump
/scr1/wab/GAMESS-UK/bin/gamess << EOF title ethylene 6-31g** MP2/ optimised total energy = -78.3272309
zmatrix angstrom c c 1 cc h 1 ch 2 hcc h 1 ch 2 hcc 3 180.0
h 2 ch 1 hcc 3 0.0
h 2 ch 1 hcc 3 180.0
variables cc 1.40
ch 1.10
hcc 118.0
end basis 6-31g** runtype optimize
17 DIRECT-MP2 CALCULATION OF PYRIDINE scftype mp2 xtol 0.0001
enter
EOF
MP2 Polarisability
#!/bin/csh -f cd /scr1/user setenv ed2 c2h4main setenv ed3 c2h4dump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title ethylene MP2/6-31g** ground state polarisability zmatrix angstrom c c 1 cc h 1 ch 2 hcc h 1 ch 2 hcc 3 180.0
h 2 ch 1 hcc 3 0.0
h 2 ch 1 hcc 3 180.0
variables cc 1.40
ch 1.10
hcc 118.0
end basis 6-31g** runtype polarisability scftype mp2 enter
EOF
34
17 Direct-MP2 Calculation of Pyridine
We show below the data for performing a direct–MP2 calculation on the C
5
H
5
N molecule, conducted in a 6–31G* basis set. Note the use of the MEMORY pre-directive in requesting a memory allocation of 4 MWords.
#!/bin/csh -f cd /scr1/user setenv ed3 pyred3
/scr1/wab/GAMESS-UK/bin/gamess << EOF title pyridine 6-31g* direct-mp2 zmat angstrom n x 1 1.0
x 1 1.0 2 90.
x 1 1.0 2 90. 3 90.
c 1 c4n 3 90. 2 180.
x 5 1.0 1 90. 3 0.0
18 CASSCF GEOMETRY OPTIMISATIONS x 5 1.0 1 90. 4 0.0
h 5 ch4 6 90. 1 180.
c 1 c2n 2 c2nz 3 180.
c 1 c2n 2 c2nz 3 0.0
c 9 c2c3 1 ccn 2 180.
c 10 c2c3 1 ccn 2 180.
h 9 c2h6 1 nch2 2 0.0
h 10 c2h6 1 nch2 2 0.0
h 11 c3h5 9 c2c3h 1 180.
h 12 c3h5 10 c2c3h 1 180.
variables c4n 2.7845546
ch4 1.0823078
c2n 1.3372389
c2nz 120.641858
c2c3 1.3944571
ccn 122.662269
c2h6 1.0814291
c3h5 1.0809550
nch2 116.400433
c2c3h 120.158516
end basis 6-31g* scftype direct mp2 enter
EOF
35
18 CASSCF Geometry Optimisations
We consider below a CASSCF calculation on the X
1
A
1 state of H
2
O, using a full valence criterion in specifying the active space so that the formally vacant SCF virtual MOs, 4a
1 and
2b
2
, are permitted variable occupancy. This example utilises the vectors from the closed shell
SCF calculation of Example 1.
#!/bin/csh -f cd /scr1/user setenv ed2 h2omain setenv ed3 h2odump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title water at casscf level 3-21g basis set zmat angstrom o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end scftype casscf config print
18 CASSCF GEOMETRY OPTIMISATIONS 36 doc 1 to 5 uoc 6 7 end superci 1 to 8 newton 9 to 20 hessian 9 to 20 simul 9 to 20 enter
EOF
The following points should be noted:
• It is not possible to use BYPASS in the above, given the data for the SCF job of Example
1. This would have resulted in generation of a P-supermatrix which is not usable in a
CASSCF run (see Part 2, Table 1).
• CASSCF calculations require two scratch FORTRAN data sets, FT01 and FT02.
In the above we have assumed that the CASSCF calculation completes in the time allocated, with the associated direct-access files allocated in default scratch status. The following job is typical of that required if restarts of the CASSCF step are envisaged:
#!/bin/csh -f cd /scr1/user setenv ed1 h2oed1 setenv ed2 h2omain setenv ed3 h2odump setenv ed4 h2oed4 setenv ed6 h2oed6 setenv ed9 h2oed9 setenv ed10 h2oed10
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title water at casscf level 3-21g basis set zmat angstrom o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end scftype casscf config print doc 1 to 5 uoc 6 7 end superci 1 to 8 newton 9 to 20 hessian 9 to 20 simul 9 to 20 enter
EOF
18 CASSCF GEOMETRY OPTIMISATIONS 37
Assuming the above job terminated prior to convergence, the calculation might be restarted as follows:
#!/bin/csh -f cd /scr1/user setenv ed1 h2oed1 setenv ed2 h2omain setenv ed3 h2odump setenv ed4 h2oed4 setenv ed6 h2oed6 setenv ed9 h2oed9 setenv ed10 h2oed10
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart scf title water at casscf level 3-21g basis set zmat angstrom o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end scftype casscf config bypass doc 1 to 5 uoc 6 7 end superci 1 to 2 newton 3 to 20 hessian 3 to 20 simul 3 to 20 vectors 6 7 enter 6 7
EOF where the default sections housing the CASSCF vectors and ci coefficients (sections 6 and 7 respectively) created in the startup job are explicitly declared above, and CONFIG processing is bypass’ed. Having completed the single point calculation, the following might be used to perform a geometry optimisation at the CASSCF level. Note that it is now necessary to SAVE the data set associated with ED11 if restarts are envisaged.
#!/bin/csh -f cd /scr1/user setenv ed1 h2oed1 setenv ed2 h2omain setenv ed3 h2odump setenv ed4 h2oed4 setenv ed6 h2oed6 setenv ed9 h2oed9 setenv ed10 h2oed10 setenv ed11 h2oed11
19 CASSCF + 2ND-ORDER CI CALCULATIONS ON BEO 38
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title water - geometry optimisation at casscf level zmat angstrom o h 1 oh h 1 oh 2 hoh variables oh 0.956
hoh 104.5
end runtype optimise scftype casscf config bypass doc 1 to 5 uoc 6 7 end superci 1 to 5 newton 6 to 20 hessian 6 to 20 simul 6 to 20 enter
EOF
Again the default CASSCF vector and CI coefficient sections from the initial energy calculation will be used by default in the optimisation job.
19 CASSCF + 2nd-order CI Calculations on BeO
First, we consider below a CASSCF calculation on the X
1
Σ
+ configuration state of BeO, characterised by the
1σ
2
2σ
2
3σ
2
4σ
2
1π
4
The initial closed–shell SCF using a DZP basis was conducted with the following job:
(1)
#!/bin/csh -f cd /scr1/user setenv ed2 beomain setenv ed3 beodump
/scr1/wab/GAMESS-UK/bin/gamess << EOF super off nosym title\beo .. dzp zmat angstrom\be\o 1 beo variables\beo 1.300 hessian 0.7\end basis dzp enter
EOF
An examination of the closed-shell SCF output reveals the following symmetry adapted basis information
19 CASSCF + 2ND-ORDER CI CALCULATIONS ON BEO 39
=============================
IRREP NO. OF SYMMETRY ADAPTED
BASIS FUNCTIONS
=============================
1
2
17
6
3
4
6
2
============================= and the SCF MO ordering shown below:
10
11
8
9
12
13
14
===============================================
M.O.
IRREP ORBITAL ENERGY ORBITAL OCCUPANCY
===============================================
3
4
1
2
5
6
7
1
1
1
1
3
2
1
-20.45769692
-4.72825831
-1.15792230
-0.46629250
-0.39257378
-0.39257378
-0.05704423
2.0000000
2.0000000
2.0000000
2.0000000
2.0000000
2.0000000
0.0000000
2
3
1
1
3
2
1
0.09936415
0.09936415
0.15573442
0.25156032
0.29518660
0.29518660
0.57290305
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
19
20
21
22
23
15
16
17
18
24
25
26
27
4
1
2
3
1
2
3
1
1
1
4
1
2
0.66957865
0.66957865
0.84348942
0.84348942
1.01733643
1.05237116
1.05237116
1.24301610
1.45883277
1.80402496
2.36534068
2.36534068
2.62307878
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
28
29
30
3
1
1
2.62307878
3.16009549
4.37857805
0.0000000
0.0000000
0.0000000
31 1 45.42979631
0.0000000
===============================================
We wish to perform a CASSCF calculation in which the inner shell and O2s orbitals (the 1σ–3σ) remain doubly occupied, with the active space including the formally vacant SCF virtual MOs, the 5σ and 2π. This example utilises the vectors from the closed shell SCF calculation. We wish to perform the CASSCF calculation under RUNTYPE CI specification where, having performed the 6 electrons in 6 orbital CASSCF, we use the natural orbitals in carrying out a second-order
CI using the Direct-CI module. Specifically we aim to use a reference space in the CI consisting
19 CASSCF + 2ND-ORDER CI CALCULATIONS ON BEO 40 of all CSFs which can be generated by distributing 6 electrons in 6 MOs i.e. the CASSCF space.
This may be achieved in a single run through the following job specification:
#!/bin/csh -f cd /scr1/user setenv ed1 beoed1 setenv ed2 beomain setenv ed3 beodump setenv ed4 beoed4 setenv ed5 beoed5 setenv ed6 beoed6 setenv ed9 beoed9 setenv ed10 beoed10
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title\beo .. dzp casscf+ci (6 electrons in 6 mos) bypass zmat angstrom\be\o 1 beo variables\beo 1.300 hessian 0.7\end basis dzp runtype ci active\4 to 31\end core\1 to 3\end scftype casscf thresh 4 config print fzc 1 to 3 doc 4 to 6 uoc 7 to 9 end superci 1 to 8 newton 9 to 20 hessian 9 to 20 simul 9 to 20 direct 6 6 22 conf
2 2 2 0 0 0 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 enter
EOF
20 MCSCF + 2ND-ORDER CI CALCULATIONS ON BEO 41
20 MCSCF + 2nd-order CI Calculations on BeO
First, we consider below a MCSCF calculation on the X
1
Σ
+ configuration state of BeO, characterised by the
1σ
2
2σ
2
3σ
2
4σ
2
1π
4
The initial closed–shell SCF using a DZP basis was conducted with the following job:
(2)
#!/bin/csh -f cd /scr1/user setenv ed2 beomain setenv ed3 beodump
/scr1/wab/GAMESS-UK/bin/gamess << EOF super off nosym title\beo .. dzp zmat angstrom\be\o 1 beo variables\beo 1.300 hessian 0.7\end basis dzp enter
EOF
An examination of the closed-shell SCF output reveals the following symmetry adapted basis information
=============================
IRREP NO. OF SYMMETRY ADAPTED
BASIS FUNCTIONS
=============================
3
4
1
2
17
6
6
2
============================= and the SCF MO ordering shown below:
10
11
12
8
9
6
7
===============================================
M.O.
IRREP ORBITAL ENERGY ORBITAL OCCUPANCY
===============================================
3
4
5
1
2
1
1
1
1
3
-20.45769692
-4.72825831
-1.15792230
-0.46629250
-0.39257378
2.0000000
2.0000000
2.0000000
2.0000000
2.0000000
1
1
3
2
3
2
1
-0.39257378
-0.05704423
0.09936415
0.09936415
0.15573442
0.25156032
0.29518660
2.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
20 MCSCF + 2ND-ORDER CI CALCULATIONS ON BEO 42
17
18
19
20
21
13
14
15
16
1
2
3
2
3
4
1
2
1
0.29518660
0.57290305
0.66957865
0.66957865
0.84348942
0.84348942
1.01733643
1.05237116
1.05237116
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
22
23
24
25
26
27
28
1
1
1
4
1
2
3
1.24301610
1.45883277
1.80402496
2.36534068
2.36534068
2.62307878
2.62307878
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
0.0000000
29
30
1
1
3.16009549
4.37857805
0.0000000
0.0000000
31 1 45.42979631
0.0000000
===============================================
We wish to perform a CASSCF calculation in which the inner shell and O2s orbitals (the 1σ–3σ) remain doubly occupied, with the active space including the formally vacant SCF virtual MOs, the 5σ and 2π. This example utilises the vectors from the closed shell SCF calculation.
#!/bin/csh -f cd /scr1/user setenv ed2 beomain setenv ed3 beodump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new super off nosym title\beo .. dzp bypass zmat angstrom\be\o 1 beo variables\beo 1.300 hessian 0.7\end basis dzp scftype mcscf thresh 4 mcscf orbital\3cor1 doc1 doc3 doc2 uoc1 uoc2 uoc3 \end enter
EOF
The following points should be noted:
• The MCSCF Natural orbitals will be routed to section 10 of the Dumpfile on convergence, the default section used for NO output.
• Integral evaluation has been bypassed as the initial SCF job specified the necessary integral format for the subsequent SCF.
20 MCSCF + 2ND-ORDER CI CALCULATIONS ON BEO 43
In the above we have assumed that the MCSCF calculation completes in the time allocated, with the associated direct-access files allocated in default scratch status. The following job is typical of that required if restarts of the MCSCF step are envisaged:
#!/bin/csh -f cd /scr1/user setenv ed2 beomain setenv ed3 beodump setenv ed4 beoed4 setenv ed6 beoed6 setenv ed13 beoed13
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new super off nosym title\beo .. dzp bypass zmat angstrom\be\o 1 beo\ variables\beo 1.300 hessian 0.7\end basis dzp scftype mcscf thresh 4 mcscf orbital\3cor1 doc1 doc3 doc2 uoc1 uoc2 uoc3 \end enter
EOF
Note that the symmetry adapted list of integrals are sorted at the outset of processing to ED13, and this file should be preserved across restart jobs, given that the DONT SORT data line is presented to the restart job. Assuming the above job terminated prior to convergence, the calculation might be restarted as follows:
#!/bin/csh -f cd /scr1/user setenv ed2 beomain setenv ed3 beodump setenv ed4 beoed4 setenv ed6 beoed6 setenv ed13 beoed13
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart scf super off nosym title\beo .. dzp zmat angstrom\be\o 1 beo variables\beo 1.300 hessian 0.7\end basis dzp scftype mcscf thresh 4 mcscf orbital\3cor1 doc1 doc3 doc2 uoc1 uoc2 uoc3 \end dont sort enter
/EOF
21 TABLE-CI CALCULATIONS ON THE AMMONIA CATION 44
Now let us consider performing the MCSCF calculation under RUNTYPE CI specification where, having performed the 6 electrons in 6 orbital CASSCF, we use the natural orbitals in carrying out a second-order CI using the Direct-CI module. Specifically we aim to use a reference space in the CI consisting of all CSFs which can be generated by distributing 6 electrons in 6 MOs i.e.
the CASSCF space. This may be achieved in a single run through the following job specification:
#!/bin/csh -f cd /scr1/user setenv ed2 beomain setenv ed3 beodump
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new super off nosym title\beo .. dzp mcscf+2nd-order ci (6 electrons in 6 mos) zmat angstrom\be\o 1 beo variables\beo 1.300 hessian 0.7\end basis dzp runtype ci active\4 to 31\end core\1 to 3\end scftype mcscf thresh 4 mcscf orbital\3cor1 doc1 doc3 doc2 uoc1 uoc2 uoc3 \end direct 6 6 22 conf
2 2 2 0 0 0 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 refgen
1 4 1 5 1 6 2 4 2 5 2 6 3 4 3 5 3 6 vectors 1\enter 20 21
EOF
Note that the vectors specification is requesting that the closed-shell SCF eigenvectors be used to initiate the MCSCF calculation. The MCSCF natural orbitals, routed to section 10 of the
Dumpfile in default, will be used as the orbitals for the Direct-CI calculation.
21 Table-CI calculations on the Ammonia Cation
We consider below a Table-CI calculation of the X
2
A
1 state and 1
2
A
1 state of the ammonia cation. In the first instance we consider performing the calculation in two steps, initially the
21 TABLE-CI CALCULATIONS ON THE AMMONIA CATION 45 open-shell SCF calculation followed by the MRD-CI 2-reference state calculation. We then subdivide the CI calculation into 5 separate steps, performing the symmetry adaption + integral transformation, followed by configuration selection, construction of the CI Hamiltonian, the diagonalisation and, finally, the subsequent analysis of the CI wavefunctions.
Open-shell SCF Job
#!/bin/csh -f cd /scr1/user setenv ed2 nh3main setenv ed3 nh3dump
/scr1/wab/GAMESS-UK/bin/gamess << EOF title nh3+ * 3-21g * scf-energy=-55.53325817 hartree super off nosym charge 1 mult 2 zmat angstrom n h 1 roh h 1 roh 2 theta h 1 roh 2 theta 3 theta 1 variables roh 1.03
hessian 0.7
theta 104.2
hessian 0.2
end enter
EOF
Table-CI Job
#!/bin/csh -f cd /scr1/user setenv ed2 nh3main setenv ed3 nh3dump setenv table TABLE
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title
* nh3+ * 3-21g * mrdci-energies 1r -55.6393336 2r -55.4116210
bypass scf charge 1 mult 2 zmat angstrom n h 1 roh h 1 roh 2 theta h 1 roh 2 theta 3 theta 1 variables roh 1.03
hessian 0.7
theta 104.2
hessian 0.2
end runtype ci mrdci
21 TABLE-CI CALCULATIONS ON THE AMMONIA CATION 46 adapt tran table select symmetry 1 spin 2 cntrl 9 conf
1 4 1 2 3 12
1 3 1 2 4 12 roots 2 thresh 5 5 ci diag extrap 3 dthr 0.0001 0.0001
natorb cive 1 2 prop cive 1 2
1 4 1 2 3 12
1 3 1 2 4 12 moment
36 1 36 2 1 enter
EOF
The orbitals employed in the CI calculation will be taken from the default section associated with the open-shell RHF module, section 5, that containing the energy-ordered canonicalised open-shell vectors written on termination of the SCF process. Note that the table keyword will activate generation of the Table-CI data base, to be used in the subsequent steps below. In this case the data base will be written to the file TABLE in /scr1 for subsequent use. A copy of this data base is available on the DEC PW433AU, and may be accessed directly, thus: setenv table /scr1/wab/GAMESS-UK/libs/TABLE
Now let us consider dividing the above CI calculation. The following points should be noted in this division:
• The SETENV lines indicate those FORTRAN data sets that must be retained between separate runs of the program. We assume below that the TABLE data-base is available from the previous job, thus omitting the TABLE step.
• Note the use of the BYPASS keyword on the various steps comprising the Table-CI procedure. Such a keyword is required on both those steps already completed and those steps to be handled in a subsequent run of the program.
Table-CI Data I. Symmetry Adaption and Integral Transformation
#!/bin/csh -f cd /scr1/user
21 TABLE-CI CALCULATIONS ON THE AMMONIA CATION setenv ed2 nh3main setenv ed3 nh3dump setenv table TABLE setenv ftn031 nh3tran
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title
* nh3+ * 3-21g * mrdci-energies 1r -55.6393336 2r -55.4116210
bypass scf charge 1 mult 2 zmat angstrom n h 1 roh h 1 roh 2 theta h 1 roh 2 theta 3 theta 1 variables roh 1.03
hessian 0.7
theta 104.2
hessian 0.2
end runtype ci mrdci adapt tran select bypass symmetry 1 spin 2 cntrl 9 conf
1 4 1 2 3 12
1 3 1 2 4 12 roots 2 thresh 5 5 ci bypass diag bypass extrap 3 dthr 0.0001 0.0001
enter
EOF
Table-CI Job II. Configuration Selection
#!/bin/csh -f cd /scr1/user setenv ed2 nh3main setenv ed3 nh3dump setenv table TABLE setenv ftn031 nh3tran setenv ftn033 nh3sel01 setenv ftn034 nh3sel02
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart ci title
* nh3+ * 3-21g * mrdci-energies 1r -55.6393336 2r -55.4116210
bypass scf
47
21 TABLE-CI CALCULATIONS ON THE AMMONIA CATION charge 1 mult 2 zmat angstrom n h 1 roh h 1 roh 2 theta h 1 roh 2 theta 3 theta 1 variables roh 1.03
hessian 0.7
theta 104.2
hessian 0.2
end runtype ci mrdci adapt bypass tran bypass select symmetry 1 spin 2 cntrl 9 conf
1 4 1 2 3 12
1 3 1 2 4 12 roots 2 thresh 5 5 ci bypass diag bypass extrap 3 dthr 0.0001 0.0001
enter
EOF
Table-CI Job III. CI Hamiltonian Construction
#!/bin/csh -f cd /scr1/user setenv ed2 nh3main setenv ed3 nh3dump setenv table TABLE setenv ftn031 nh3tran setenv ftn033 nh3sel01 setenv ftn034 nh3sel02 setenv ftn035 nh3ham
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart ci title
* nh3+ * 3-21g * mrdci-energies 1r -55.6393336 2r -55.4116210
bypass scf charge 1 mult 2 zmat angstrom n h 1 roh h 1 roh 2 theta h 1 roh 2 theta 3 theta 1 variables
48
21 TABLE-CI CALCULATIONS ON THE AMMONIA CATION roh 1.03
hessian 0.7
theta 104.2
hessian 0.2
end runtype ci mrdci adapt bypass tran bypass select bypass symmetry 1 spin 2 cntrl 9 conf
1 4 1 2 3 12
1 3 1 2 4 12 roots 2 thresh 5 5 ci diag bypass extrap 3 dthr 0.0001 0.0001
enter
EOF
Table-CI Job IV. Diagonalisation
#!/bin/csh -f cd /scr1/user setenv ed2 nh3main setenv ed3 nh3dump setenv ftn035 nh3ham setenv ftn036 nh3diag
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart ci title
* nh3+ * 3-21g * mrdci-energies 1r -55.6393336 2r -55.4116210
bypass scf charge 1 mult 2 zmat angstrom n h 1 roh h 1 roh 2 theta h 1 roh 2 theta 3 theta 1 variables roh 1.03
hessian 0.7
theta 104.2
hessian 0.2
end runtype ci mrdci adapt bypass tran bypass select bypass symmetry 1 spin 2 cntrl 9
49
21 TABLE-CI CALCULATIONS ON THE AMMONIA CATION conf
1 4 1 2 3 12
1 3 1 2 4 12 roots 2 thresh 5 5 ci bypass diag extrap 3 dthr 0.0001 0.0001
enter
EOF
Table-CI Job V. CI Wavefunction Analysis
#!/bin/csh -f cd /scr1/user setenv ed2 nh3main setenv ed3 nh3dump setenv ftn036 nh3diag
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart ci title
* nh3+ * 3-21g * mrdci-energies 1r -55.6393336 2r -55.4116210
bypass scf charge 1 mult 2 zmat angstrom n h 1 roh h 1 roh 2 theta h 1 roh 2 theta 3 theta 1 variables roh 1.03
hessian 0.7
theta 104.2
hessian 0.2
end runtype ci mrdci adapt bypass tran bypass select bypass symmetry 1 spin 2 cntrl 9 conf
1 4 1 2 3 12
1 3 1 2 4 12 roots 2 thresh 5 5 ci bypass diag bypass extrap 3 dthr 0.0001 0.0001
natorb cive 1 2 prop
50
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2 cive 1 2
1 4 1 2 3 12
1 3 1 2 4 12 moment
36 1 36 2 1 enter
EOF
51
22 ECP, CASSCF and Direct-CI Calculations on NiCCH
2
This example illustrates the use of CASSCF and Direct-CI calculations in the framework of
ECP studies. The molecular system under investigation is NiCCH
2
, with a 5-reference direct-CI calculation performed using a CASSCF wavefunction for the lowest triplet state. Five data files are presented below:
1. Start–up closed–shell SCF calculation for the
1
A
1 state. Note the SUPER directive for compatibility with the subsequent open–shell calculation. The ECP library file
/scr1/wab/GAMESS-UK/libs/ecplib is allocated to LFN ed0, with the NIHAY and C non-local ECPs requested under control of the PSEUDO directive.
2. Restart SCF job, with appropriate use of the SWAP directive to converge the closed–shell
SCF.
3. RHF calculation for the
3
A
1 state.
4. CASSCF calculation for the
3
A
1 state.
5. 5-reference Direct-CI calculation for the
3
A
1 state.
Closed-shell SCF Start-up Job
#!/bin/csh -f cd /scr1/user setenv ed2 mainnips setenv ed3 dumpnips setenv ed0 /scr1/wab/GAMESS-UK/libs/ecplib
/scr1/wab/GAMESS-UK/bin/gamess << EOF title ni(cch2) 1a1 rhf ,hay’s ni, bar’s nm ecp’s mult 1 super force zmat angstrom ni c 1 nica x 2 1.0 1 90.0
c 2 cacb 3 90.0 1 180.0
x 4 1.0 2 90.0 3 0.0
h 4 hcb 2 hcc 5 90.0
h 4 hcb 2 hcc 5 -90.0
variables nica 2.0895
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2 cacb 1.3604
hcb 1.1047
hcc 122.646
end basis s h
0.032828
0.231208
0.817238
s h
1.000000
s c
1.000000
s c
1.000000
p c
13.3615
2.0133
0.4538
0.1233
0.4962
0.1533
0.018534
0.115442
0.386206
0.640089
18.1557
3.9864
1.1429
0.3594
p c
1.000000
0.1146
s ni
-0.4372528 0.6778
1.1889453 0.1116
s ni
1.0000000 0.0387
p ni
1.0000000 0.0840
p ni
1.0000000 0.0240
d ni
0.0360414 42.7200
0.1938645 11.7600
0.4596238 3.8170
0.5599305 1.1690
d ni
1.0000000 0.2836
end pseudo nonlocal nihay ni c c maxcyc 30 level 2.5 15 1.0
vectors hcore enter
EOF
Closed-shell SCF Restart Data
#!/bin/csh -f cd /scr1/user setenv ed2 mainnips setenv ed3 dumpnips setenv ed0 /scr1/wab/GAMESS-UK/libs/ecplib
52
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title ni(cch2) 1a1 rhf restart ,hay’s ni, bar’s nm ecp’s mult 1 bypass super force zmat angstrom ni c 1 nica x 2 1.0 1 90.0
c 2 cacb 3 90.0 1 180.0
x 4 1.0 2 90.0 3 0.0
h 4 hcb 2 hcc 5 90.0
h 4 hcb 2 hcc 5 -90.0
variables nica 2.0895
cacb 1.3604
hcb 1.1047
hcc 122.646
end basis s h
0.032828
0.231208
13.3615
2.0133
0.4538
0.817238
s h
1.000000
s c
1.000000
s c
1.000000
0.1233
0.4962
0.1533
p c
0.018534
0.115442
0.386206
18.1557
3.9864
1.1429
0.3594
0.640089
p c
1.000000
s ni
0.1146
-0.4372528 0.6778
1.1889453 0.1116
s ni
1.0000000 0.0387
p ni
1.0000000 0.0840
p ni
1.0000000 0.0240
d ni
0.0360414 42.7200
0.1938645 11.7600
0.4596238 3.8170
0.5599305 1.1690
d ni
1.0000000 0.2836
53
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2 end pseudo nonlocal nihay ni c c maxcyc 40 level 3.0 10 1.0
swap
4 5
6 8
8 10
10 11 end enter
EOF
Open-shell SCF Job
#!/bin/csh -f cd /scr1/user setenv ed2 mainnips setenv ed3 dumpnips setenv ed0 /scr1/wab/GAMESS-UK/libs/ecplib
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title ni(cch2) 3a1 rhf ,hay’s ni, bar’s nm ecp’s mult 3 super force bypass zmat angstrom ni c 1 nica x 2 1.0 1 90.0
c 2 cacb 3 90.0 1 180.0
x 4 1.0 2 90.0 3 0.0
h 4 hcb 2 hcc 5 90.0
h 4 hcb 2 hcc 5 -90.0
variables nica 2.0895
cacb 1.3604
hcb 1.1047
hcc 122.646
end basis s h
0.032828
0.231208
0.817238
s h
1.000000
s c
13.3615
2.0133
0.4538
0.1233
1.000000
s c
1.000000
p c
0.4962
0.1533
54
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2
55
0.018534
0.115442
0.386206
0.640089
18.1557
3.9864
1.1429
0.3594
p c
1.000000
0.1146
s ni
-0.4372528 0.6778
1.1889453 0.1116
s ni
1.0000000 0.0387
p ni
1.0000000 0.0840
p ni
1.0000000 0.0240
d ni
0.0360414 42.7200
0.1938645 11.7600
0.4596238 3.8170
0.5599305 1.1690
d ni
1.0000000 0.2836
end pseudo nonlocal nihay ni c c scftype gvb maxcyc 50 level 2.0 3.0 15 1.0 1.0
open 2 2 swap
11 12
14 15 end enter
EOF
Eigenvector utilisation in the above job will drive off the default sections of the Dumpfile, with the open-shell SCF module using the closed-shell SCF vectors from section 1 to initiate the SCF process, and writing the SCF open-shell orbitals to sections 4 and 5 (the energy-ordered SCF
MOs). These latter orbitals will be used below to instigate the CASSCF processing.
CASSCF Job
#!/bin/csh -f cd /scr1/user setenv ed2 mainnips setenv ed3 dumpnips setenv ed0 /scr1/wab/GAMESS-UK/libs/ecplib setenv ed6 trannips setenv ed4 lfornips
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2 ni(cch2) 3a1 c2v cas at opt (3 2 2 0), hay’s ni, bar’s nm ecp’s mult 3 super off nosym zmat angstrom ni c 1 nica x 2 1.0 1 90.0
c 2 cacb 3 90.0 1 180.0
x 4 1.0 2 90.0 3 0.0
h 4 hcb 2 hcc 5 90.0
h 4 hcb 2 hcc 5 -90.0
variables nica 2.0895
cacb 1.3604
hcb 1.1047
hcc 122.646
end basis s h
0.032828
0.231208
0.817238
s h
1.000000
s c
13.3615
2.0133
0.4538
0.1233
1.000000
s c
1.000000
p c
0.018534
0.115442
0.386206
0.4962
0.1533
18.1557
3.9864
1.1429
0.3594
0.640089
p c
1.000000
s ni
0.1146
-0.4372528 0.6778
1.1889453 0.1116
s ni
1.0000000 0.0387
p ni
1.0000000 0.0840
p ni
1.0000000 0.0240
d ni
0.0360414 42.7200
0.1938645 11.7600
0.4596238 3.8170
0.5599305 1.1690
d ni
1.0000000 0.2836
end pseudo nonlocal nihay ni c c
56
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2 scftype casscf config print fzc 1 to 7 doc 8 to 9 alp 10 to 11 uoc 12 to 14 end superci 1 to 12 newton 13 to 20 hessian 13 to 20 simul 15 to 20 vectors 5 swap
14 15 end enter
EOF
Direct-CI Job
#!/bin/csh -f cd /scr1/user setenv ed2 mainnips setenv ed3 dumpnips setenv ed0 /scr1/wab/GAMESS-UK/libs/ecplib setenv ed5 cinips setenv ed6 trannips
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart new title ni(cch2) 3a1 mrsdci (3 2 2 0) ,hay’s ni, bar’s nm ecp’s mult 3 super off nosym bypass scf zmat angstrom ni c 1 nica x 2 1.0 1 90.0
c 2 cacb 3 90.0 1 180.0
x 4 1.0 2 90.0 3 0.0
h 4 hcb 2 hcc 5 90.0
h 4 hcb 2 hcc 5 -90.0
variables nica 2.0895
cacb 1.3604
hcb 1.1047
hcc 122.646
end basis s h
0.032828
0.231208
0.817238
s h
1.000000
13.3615
2.0133
0.4538
0.1233
57
22 ECP, CASSCF AND DIRECT-CI CALCULATIONS ON NICCH
2 s c
1.000000
s c
1.000000
p c
0.018534
0.115442
0.386206
0.640089
0.4962
0.1533
18.1557
3.9864
1.1429
0.3594
p c
1.000000
0.1146
s ni
-0.4372528 0.6778
1.1889453 0.1116
s ni
1.0000000 0.0387
p ni
1.0000000 0.0840
p ni
1.0000000 0.0240
d ni
0.0360414 42.7200
0.1938645 11.7600
0.4596238 3.8170
0.5599305 1.1690
d ni
1.0000000 0.2836
end pseudo nonlocal nihay ni c c runtype ci core end active
1 to 40 end scftype casscf config print fzc 1 to 7 doc 8 to 9 alp 10 to 11 uoc 12 to 14 end superci 1 to 12 newton 13 to 20 hessian 13 to 20 simul 15 to 20 direct 20 14 26 spin triplet conf
2 2 2 2 2 2 2 2 2 1 1 0 0 0
2 2 2 2 2 2 2 2 1 2 0 0 1 0
2 2 2 2 2 2 2 2 1 1 1 0 1 0
2 2 2 2 2 2 2 2 0 1 1 0 2 0
58
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE59
2 2 2 2 2 2 2 1 2 2 0 1 0 0
2 2 2 2 2 2 2 1 2 1 1 1 0 0 vprint 100 0.01
maxcyc 10 enter
EOF
23 Table-CI Calculations of the Electronic Spectra of Pyridine
This example demonstrates the use of the Table-CI module in the calculation of the low-lying states of Pyridine. Specifically, we are involved in determining the disposition of the first ten
1
A
1 and
1
A
2 states, using a common set of orbitals (the X
1
A
1
SCF-MOs) in a DZ plus Rydberg basis set of 91 functions. Five job files are presented below:
1. Start–up closed–shell SCF calculation for the X
1
A
1 state. Note the SUPER directive for compatibility with the subsequent CI calculation. Note also the particular syntax for siting the DZ basis on H: the third and fourth data fields are to provide an unscaled hydrogen basis, since the default specification will scale the two components by 1.2 (the more contracted) and 1.15 (the more diffuse component)
2. 1M/1R Table-CI calculation of the X
1
A
1 state.
3. 6M/1R Table-CI calculation of the X
1
A
1 state.
4. 21M/10R Table-CI calculation of the ten lowest
1
A
1 states.
5. 19M/10R Table-CI calculation of the ten lowest
1
A
2 states.
1. Closed-shell SCF Job
#!/bin/csh -f cd /scr1/user setenv ed2 pyred2 setenv ed3 pyred3
/scr1/wab/GAMESS-UK/bin/gamess << EOF title pyridine dz+bond-centred functions super off nosym zmat angstrom n x 1 1.0
x 1 1.0 2 90.
x 1 1.0 2 90. 3 90.
c 1 c4n 3 90. 2 180.
x 5 1.0 1 90. 3 0.0
x 5 1.0 1 90. 4 0.0
h 5 ch4 6 90. 1 180.
c 1 c2n 2 c2nz 3 180.
c 1 c2n 2 c2nz 3 0.0
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE60 c 9 c2c3 1 ccn 2 180.
c 10 c2c3 1 ccn 2 180.
h 9 c2h6 1 nch2 2 0.0
h 10 c2h6 1 nch2 2 0.0
h 11 c3h5 9 c2c3h 1 180.
h 12 c3h5 10 c2c3h 1 180.
bq 1 1.39 3 90. 2 180.
variables c4n 2.7845546
ch4 1.0823078
c2n 1.3372389
c2nz 120.641858
c2c3 1.3944571
ccn 122.662269
c2h6 1.0814291
c3h5 1.0809550
nch2 116.400433
c2c3h 120.158516
end basis dz h 1.0 1.0
dz n dz c s bq
1.0 0.021
s bq
1.0 0.008
s bq
1.0 0.0025
p bq
1.0 0.017
p bq
1.0 0.009
d bq
1.0 0.015
d bq
1.0 0.008
end enter
EOF
2. 1M/1R Table-CI Job for the X
1
A
1
State
An examination of the SCF output reveals the following symmetry adapted basis functions, given the C
2v geometry and DZ plus Rydberg basis set:
=============================
IRREP NO. OF SYMMETRY ADAPTED
BASIS FUNCTIONS
=============================
1 45
2
3
4
12
28
6
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE61
=============================
Thus the orbital reordering performed by the Table-CI module will yield the sequence numbers
1–45 for the a
1
MOs, 46–57 for the b
1
MOs, 58–85 for the b
2
MOs and 86–91 for the a
2
MOs.
We are both freezing and discarding orbitals in the subsequent CI calculations. Confining this to both a
1 and b
2
MOs, the first six orbitals of a
1 symmetry and first four orbitals of b
2 symmetry are to be frozen, and the eight highest energy orbitals of a
1 symmetry and six highest of b
2 are to be discarded. Thus the final sequence numbers for the active orbitals in the CI are 1–31 for the a
1
MOs, 32–43 for the b
1
MOs, 44–61 for the b
2
MOs and 62–68 for the a
2
MOs.
The CONF data line specifying the reference configuration is based on the associated sequence numbers of these active orbitals.
#!/bin/csh -f cd /scr1/user setenv ed2 pyred2 setenv ed3 pyred3 setenv ftn031 pyrtran setenv table /scr1/wab/GAMESS-UK/libs/TABLE
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title pyridine dz+bond-centred functions super off nosym bypass scf zmat angstrom n x 1 1.0
x 1 1.0 2 90.
x 1 1.0 2 90. 3 90.
c 1 c4n 3 90. 2 180.
x 5 1.0 1 90. 3 0.0
x 5 1.0 1 90. 4 0.0
h 5 ch4 6 90. 1 180.
c 1 c2n 2 c2nz 3 180.
c 1 c2n 2 c2nz 3 0.0
c 9 c2c3 1 ccn 2 180.
c 10 c2c3 1 ccn 2 180.
h 9 c2h6 1 nch2 2 0.0
h 10 c2h6 1 nch2 2 0.0
h 11 c3h5 9 c2c3h 1 180.
h 12 c3h5 10 c2c3h 1 180.
bq 1 1.39 3 90. 2 180.
variables c4n 2.7845546
ch4 1.0823078
c2n 1.3372389
c2nz 120.641858
c2c3 1.3944571
ccn 122.662269
c2h6 1.0814291
c3h5 1.0809550
nch2 116.400433
c2c3h 120.158516
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE62 end basis dz h 1.0 1.0
dz n dz c s bq
1.0 0.021
s bq
1.0 0.008
s bq
1.0 0.0025
p bq
1.0 0.017
p bq
1.0 0.009
d bq
1.0 0.015
d bq
1.0 0.008
end runtype ci mrdci adapt tran freeze discard
6 0 4 0
1 to 6 1 to 4
8 0 6 0
38 to 45 23 to 28 select cntrl 22 spin singlet symmetry 1 conf
0 1 2 3 4 5 32 33 44 45 46 62 roots 1 1 thresh 30 10 ci diag title pyridine 1m1r ground state dz + 3s2p2d rydberg basis extrap 3 natorb civec 1 putq aos 2 enter
EOF
3. 6M/1R Table-CI Job for the X
1
A
1
State
#!/bin/csh -f cd /scr1/user setenv ed2 pyred2 setenv ed3 pyred3 setenv ftn031 pyrtran setenv table /scr1/wab/GAMESS-UK/libs/TABLE
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE63
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title pyridine dz+bond-centred functions super off nosym bypass scf zmat angstrom n x 1 1.0
x 1 1.0 2 90.
x 1 1.0 2 90. 3 90.
c 1 c4n 3 90. 2 180.
x 5 1.0 1 90. 3 0.0
x 5 1.0 1 90. 4 0.0
h 5 ch4 6 90. 1 180.
c 1 c2n 2 c2nz 3 180.
c 1 c2n 2 c2nz 3 0.0
c 9 c2c3 1 ccn 2 180.
c 10 c2c3 1 ccn 2 180.
h 9 c2h6 1 nch2 2 0.0
h 10 c2h6 1 nch2 2 0.0
h 11 c3h5 9 c2c3h 1 180.
h 12 c3h5 10 c2c3h 1 180.
bq 1 1.39 3 90. 2 180.
variables c4n 2.7845546
ch4 1.0823078
c2n 1.3372389
c2nz 120.641858
c2c3 1.3944571
ccn 122.662269
c2h6 1.0814291
c3h5 1.0809550
nch2 116.400433
c2c3h 120.158516
end basis dz h 1.0 1.0
dz n dz c s bq
1.0 0.021
s bq
1.0 0.008
s bq
1.0 0.0025
p bq
1.0 0.017
p bq
1.0 0.009
d bq
1.0 0.015
d bq
1.0 0.008
end
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE64 runtype ci mrdci adapt bypass tran freeze discard bypass
6 0 4 0
1 to 6 1 to 4
8 0 6 0
38 to 45 23 to 28 select cntrl 22 spin singlet symmetry 1 conf
0 1 2 3 4 5 32 33 44 45 46 62
0 1 2 3 4 5 32 38 44 45 46 62
0 1 2 3 4 5 32 33 44 45 46 65
4 32 33 38 39 1 2 3 4 5 44 45 46 62
4 32 39 62 65 1 2 3 4 5 33 44 45 46
4 33 38 62 65 1 2 3 4 5 32 44 45 46 roots 1 1 thresh 30 10 ci diag title pyridine 6m1r ground state dz + 3s2p2d rydberg basis extrap 3 natorb civec 1 putq aos 2 enter
EOF
4. 21M/10R Table-CI Job for the
1
A
1
States
#!/bin/csh -f cd /scr1/user setenv ed2 pyred2 setenv ed3 pyred3 setenv ftn031 pyrtran setenv table /scr1/wab/GAMESS-UK/libs/TABLE
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title pyridine dz+rydberg basis super off nosym bypass scf zmat angstrom n x 1 1.0
x 1 1.0 2 90.
x 1 1.0 2 90. 3 90.
c 1 c4n 3 90. 2 180.
x 5 1.0 1 90. 3 0.0
x 5 1.0 1 90. 4 0.0
h 5 ch4 6 90. 1 180.
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE65 c 1 c2n 2 c2nz 3 180.
c 1 c2n 2 c2nz 3 0.0
c 9 c2c3 1 ccn 2 180.
c 10 c2c3 1 ccn 2 180.
h 9 c2h6 1 nch2 2 0.0
h 10 c2h6 1 nch2 2 0.0
h 11 c3h5 9 c2c3h 1 180.
h 12 c3h5 10 c2c3h 1 180.
bq 1 1.39 3 90. 2 180.
variables c4n 2.7845546
ch4 1.0823078
c2n 1.3372389
c2nz 120.641858
c2c3 1.3944571
ccn 122.662269
c2h6 1.0814291
c3h5 1.0809550
nch2 116.400433
c2c3h 120.158516
end basis dz h 1.0 1.0
dz n dz c s bq
1.0 0.021
s bq
1.0 0.008
s bq
1.0 0.0025
p bq
1.0 0.017
p bq
1.0 0.009
d bq
1.0 0.015
d bq
1.0 0.008
end runtype ci mrdci adapt bypass tran freeze discard bypass
6 0 4 0
1 to 6 1 to 4
8 0 6 0
38 to 45 23 to 28 select cntrl 22 spin singlet symmetry 1 conf
2 62 65 1 2 3 4 5 32 33 44 45 46
2 33 34 1 2 3 4 5 32 44 45 46 62
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE66
2 5 8 1 2 3 4 32 33 44 45 46 62
2 62 63 1 2 3 4 5 32 33 44 45 46
2 33 38 1 2 3 4 5 32 44 45 46 62
2 33 35 1 2 3 4 5 32 44 45 46 62
2 5 7 1 2 3 4 32 33 44 45 46 62
2 33 37 1 2 3 4 5 32 44 45 46 62
2 5 9 1 2 3 4 32 33 44 45 46 62
2 62 64 1 2 3 4 5 32 33 44 45 46
2 33 36 1 2 3 4 5 32 44 45 46 62
2 5 11 1 2 3 4 32 33 44 45 46 62
2 33 39 1 2 3 4 5 32 44 45 46 62
2 32 34 1 2 3 4 5 33 44 45 46 62
2 32 38 1 2 3 4 5 33 44 45 46 62
4 5 8 33 38 1 2 3 4 32 44 45 46 62
4 33 38 62 65 1 2 3 4 5 32 44 45 46
4 32 33 34 38 1 2 3 4 5 44 45 46 62
4 33 34 62 65 1 2 3 4 5 32 44 45 46
4 32 38 62 63 1 2 3 4 5 33 44 45 46
4 5 7 33 38 1 2 3 4 32 44 45 46 62 roots 10 1 2 3 4 5 6 7 8 9 10 thresh 30 10 ci diag title pyridine 21m10r 1a1 extrap 3 enter
EOF dz + 3s2p2d rydberg basis
5. 19M/10R Table-CI Job for the
1
A
2
States
#!/bin/csh -f cd /scr1/user setenv ed2 pyred2 setenv ed3 pyred3 setenv ftn031 pyrtran setenv table /scr1/wab/GAMESS-UK/libs/TABLE
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart title pyridine dz+rydberg basis super off nosym bypass scf zmat angstrom n x 1 1.0
x 1 1.0 2 90.
x 1 1.0 2 90. 3 90.
c 1 c4n 3 90. 2 180.
x 5 1.0 1 90. 3 0.0
x 5 1.0 1 90. 4 0.0
h 5 ch4 6 90. 1 180.
c 1 c2n 2 c2nz 3 180.
c 1 c2n 2 c2nz 3 0.0
c 9 c2c3 1 ccn 2 180.
23 TABLE-CI CALCULATIONS OF THE ELECTRONIC SPECTRA OF PYRIDINE67 c 10 c2c3 1 ccn 2 180.
h 9 c2h6 1 nch2 2 0.0
h 10 c2h6 1 nch2 2 0.0
h 11 c3h5 9 c2c3h 1 180.
h 12 c3h5 10 c2c3h 1 180.
bq 1 1.39 3 90. 2 180.
variables c4n 2.7845546
ch4 1.0823078
c2n 1.3372389
c2nz 120.641858
c2c3 1.3944571
ccn 122.662269
c2h6 1.0814291
c3h5 1.0809550
nch2 116.400433
c2c3h 120.158516
end basis dz h 1.0 1.0
dz n dz c s bq
1.0 0.021
s bq
1.0 0.008
s bq
1.0 0.0025
p bq
1.0 0.017
p bq
1.0 0.009
d bq
1.0 0.015
d bq
1.0 0.008
end runtype ci mrdci adapt bypass tran freeze discard bypass
6 0 4 0
1 to 6 1 to 4
8 0 6 0
38 to 45 23 to 28 select cntrl 22 spin singlet symmetry 4 conf
2 5 65 1 2 3 4 32 33 44 45 46 62
2 33 47 1 2 3 4 5 32 44 45 46 62
2 5 63 1 2 3 4 32 33 44 45 46 62
2 33 48 1 2 3 4 5 32 44 45 46 62
2 8 62 1 2 3 4 5 32 33 44 45 46
24 FULL-CI CALCULATIONS 68
2 7 62 1 2 3 4 5 32 33 44 45 46
2 33 50 1 2 3 4 5 32 44 45 46 62
2 5 64 1 2 3 4 32 33 44 45 46 62
2 33 49 1 2 3 4 5 32 44 45 46 62
2 6 62 1 2 3 4 5 32 33 44 45 46
4 5 33 38 65 1 2 3 4 32 44 45 46 62
4 5 33 38 63 1 2 3 4 32 44 45 46 62
4 33 47 62 65 1 2 3 4 5 32 44 45 46
4 5 33 34 65 1 2 3 4 32 44 45 46 62
4 7 33 38 62 1 2 3 4 5 32 44 45 46
4 33 47 62 63 1 2 3 4 5 32 44 45 46
4 8 33 38 62 1 2 3 4 5 32 44 45 46
4 5 33 34 63 1 2 3 4 32 44 45 46 62
4 33 48 62 63 1 2 3 4 5 32 44 45 46 roots 10 1 2 3 4 5 6 7 8 9 10 thresh 30 10 ci diag title pyridine 19m10r 1a2 dz + 3s2p2d rydberg basis extrap 3 enter
EOF
24 Full-CI calculations
We consider below Full-CI calculations of the X
1
A
1 state of the H
2
O molecule. In the first instance we consider correlating all electrons. We then perform a valence-only calculation, freezing the O1s orbital through the ACTIVE and CORE directives, specifying a total of 8 electrons on the FULLCI data line.
All-electron Job
#!/bin/csh -f cd /scr1/user setenv ed2 h2omain setenv ed3 h2odump setenv ed6 h2otran setenv ftn008 file8
/scr1/wab/GAMESS-UK/bin/gamess << EOF title h2o - DZ basis - full-ci super off nosym zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end basis dz runtype ci\fullci 14 5 5 enter
EOF
Assuming the above job did not complete in the time allocated, and dumped to disk in a controlled fashion, the following job would act to continue the processing, assuming that the FOR-
24 FULL-CI CALCULATIONS 69
TRAN file file8 had been saved, along with the Mainfile, Dumpfile and Transformed integral file.
Restarting the Full-CI job
#!/bin/csh -f cd /scr1/user setenv ed2 h2omain setenv ed3 h2odump setenv ed6 h2otran setenv ftn008 file8
/scr1/wab/GAMESS-UK/bin/gamess << EOF restart ci title h2o - DZ basis - restart full-ci super off nosym zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end basis dz runtype ci\fullci 14 5 5 enter
EOF
Valence-electron Job
#!/bin/csh -f cd /scr1/user setenv ed2 h2omain setenv ed3 h2odump setenv ftn008 file8
/scr1/wab/GAMESS-UK/bin/gamess << EOF core 8000000 restart new title h2o - DZ basis - valence full-ci super off nosym bypass zmat angstrom\o\h 1 roh\h 1 roh 2 theta variables\roh 0.956 hess 0.7\theta 104.5 hess 0.2 \end basis dz runtype ci active\2 to 14 end\core\1\end fullci 13 4 4 enter
EOF
The following points should be noted:
• the use of setenv to allocate the FORTRAN stream ftn008;
• the use of the core pre-directive to specify memory requirements.
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Key features
Single Point SCF Calculations
Geometry Optimizations
Transition State Location
Force Constant Evaluation
Graphical Analysis
Direct-SCF Calculations
CASSCF Geometry Optimizations
MP2 Calculations
Table-CI Calculations
ECP Calculations
Frequently asked questions
GAMESS-UK can perform single-point SCF calculations, geometry optimizations, transition state locations, force constant evaluations, graphical analysis, direct-SCF calculations, CASSCF geometry optimizations, MP2 calculations, table-CI calculations, and ECP calculations.
GAMESS–UK reads from stdin and writes to stdout, so both input and output may be controlled by the standard means.
You can route direct access files either by using the 'cd' command at the outset of your job script to execute the job in the required directory, or through the 'setenv' command.