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Software Introduction
MOLCAS |
MOLCAS is a modular program for performing electronic structure calculations. The major strength of the package is treating electron correlation accurately by using methods based on Multi Configurational approaches and many body perturbation theory. Dynamic correlation energy of a molecular system can be calculated using the CASPT2 program module in MOLCAS. A CASPT2 calculation gives a second order perturbation estimate of the full CI energy using the Complete Active Space Self-Consistent Field (CASSCF) wavefunction of the system. New feature in version 6 includes closed and open-shell (UHF and ROHF) DFT calculations. A large number of functionals have been implemented and geometry optimization is possible using analytical gradients. MOLCAS contains a set of ab initio quantum chemical programs that are essentially separate entities, but they are connected by a shell (AUTO). Information between the programs is exchanged through files. The shell is flexible and allows the user to perform any calculation possible within the limitations of the various codes supplied with MOLCAS. To set up a calculation using MOLCAS, care must be taken to select which programs to use, then prepare input for these programs, and construct a procedure file to run the programs. The order of specifying the programs used is important, as certain programs must be run prior to running a particular program. The shell will run the MOLCAS programs sequentially in the order they appear in the general input file. Below is the program modules dependencies flowchart (extracted from the MOLCAS 6.4 User Manual).
There are basis sets implemented into the program including Effective Core Potentials (ECPs), but it is possible to specify your own basis set. Please refer to the User Manual for details. It is also possible to order basis set in MOLCAS format from the EMSL Gaussian Basis Set Order Form. The program is driven by keywords, with additional sub keywords where applicable. All numerical inputs are read in free formats. The keywords are not case sensitive. Comment lines can be added to the input by specifying an asterisk (*) in the first position of the line. Note that comments cannot be added in between a keyword and its additional specifications. All inputs begin with a namelist before the keywords and end with the keyword End of Input. The program only need to read in the first four characters of a keyword in most cases, however, it is recommended that the full keyword name is to be written for clarity. It should be noted that MOLCAS is not a black box tool. There is a detailed user manual available for MOLCAS and is accessible via the MOLCAS website. The user manual contains a tutorial with examples, and should provide an illustration of the applications of MOLCAS. The MOLCAS output files are self-explanatory, with units specified in atomic units. In some cases, files in MOLDEN format will be generated automatically which can be used to visualise molecular orbitals. |
Examples |
Example 1. Geometry Optimisation of Water Example 2. CASPT2 Calculation of Water Note: All explanations are given in red. |
| Example 1. Geometry Optimisation of NH3
The following example is a geometry optimisation at SCF level. The programs inputs must be specified in the correct order. In this example, it will read in the input for SEWARD, SCF, ALASKA and SLAPAF and will link the corresponding exchange files that are needed between the program modules automatically. SEWARD computes the one- and two-electron integrals for the molecule and basis set specified in the SEWARD section of the input. SCF than use the one- and two-electron integrals from SEWARD to determine the SCF energy. The analytical derivative program ALASKA which computes the gradient for optimised wavefunctions, is used to obtain the stationary points on the energy surfaces. The first order derivative matrix with respect to the nuclei and an approximate guess of the Hessian matrix is derived. The program SLAPAF is then used to optimise molecular structures. |
Input |
ex1.input
&SEWARD &END Title Title linie NH3, planar Symmetry Symmetry specification Z Basis Set Basis set specification N.ANO-L...4s3p2d. Requesting ANO-L for Nitrogen N .0000000000 .0000000000 .0000000000 End of Basis Basis set H.ANO-L...3s2p. Requesting ANO-L for Hydrogen H1 1.9520879910 .0000000000 .0000000000 H2 -.9760439955 1.6905577906 .0000000000 H3 -.9760439955 -1.6905577906 .0000000000 End of Basis End of Input &SCF &END Title NH3, planar Occupied Specifies the number of occupied orbitals in each of the irreducible representations 4 1 Iterations Specifies the maximum number of iterations for the SCF cycle 40 End of Input &ALASKA &END This computes the integral derivatives which are used by SLAPAF to iterate to the lowest geometry End of input &SLAPAF &END Iterations Specifies the maximum number of iterations in the relaxation procedure 20 End of input Input file (gzipped) structure.input can be downloaded here. |
Output |
ex1.out
^^^^^ M O L C A S
^^^^^^^ version 6.4 patchlevel 099
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Copyright, all rights, reserved:
Permission is hereby granted to use
but not to reproduce or distribute any part of this
program. The use is restricted to research purposes only.
Lund University Sweden, 2006.
For the author list and the recommended citation consult section 1.5 of the MOLCAS user's guide.
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module SEWARD with 256 MB of memory
at 16:20:06 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
The SQUARE option is obsolete and is ignored!
The SQUARE option is obsolete and is ignored!
SEWARD will generate:
Multipole Moment integrals up to order 2
Kinetic Energy integrals
Nuclear Attraction integrals
One-Electron Hamiltonian integrals
Two-Electron Repulsion integrals
Title:
NH3, planar
--- Group Generators ---
Reflection in the xy-plane
Integrals are discarded if absolute value <: 0.10E-13
Integral cutoff threshold is set to <: 0.10E-15
Character Table for Cs
E s(xy)
a' 1 1 x, y, xy, Rz
a" 1 -1 z, xz, Ry, yz, Rx, I
Unitary symmetry adaptation
Basis set label:N.ANO-L...4S3P2D.
Valence basis set:
==================
Associated Effective Charge 7.000000 au
Associated Actual Charge 7.000000 au
Shell nPrim nBasis Cartesian Spherical Contaminant
s 14 4 X
p 9 3 X
d 4 2 X
Basis set label:H.ANO-L...3S2P.
Valence basis set:
==================
Associated Effective Charge 1.000000 au
Associated Actual Charge 1.000000 au
Shell nPrim nBasis Cartesian Spherical Contaminant
s 8 3 X
p 4 2 X
************************************************
**** Cartesian Coordinates / Bohr, Angstrom ****
************************************************
Center Label x y z x y z
1 N 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
2 H1 2.000000 0.000000 0.000000 1.058354 0.000000 0.000000
3 H2 -0.976044 1.690558 0.000000 -0.516500 0.894605 0.000000
4 H3 -0.976044 -1.690558 0.000000 -0.516500 -0.894605 0.000000
***************************************
**** InterNuclear Distances / Bohr ****
***************************************
1 N 2 H1 3 H2 4 H3
1 N 0.000000
2 H1 2.000000 0.000000
3 H2 1.952088 3.422692 0.000000
4 H3 1.952088 3.422692 3.381116 0.000000
*******************************************
**** InterNuclear Distances / Angstrom ****
*******************************************
1 N 2 H1 3 H2 4 H3
1 N 0.000000
2 H1 1.058354 0.000000
3 H2 1.033000 1.811211 0.000000
4 H3 1.033000 1.811211 1.789209 0.000000
**************************************
**** Valence Bond Angles / Degree ****
**************************************
Atom centers Phi
2 H1 1 N 3 H2 120.00
2 H1 1 N 4 H3 120.00
3 H2 1 N 4 H3 120.00
Basis set specifications :
Symmetry species a' a"
Basis functions 37 13
Nuclear Potential Energy 11.55190353 au
--- Stop Module: seward at Fri May 19 16:20:19 BST 2006 /rc= 0 ---
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module SCF with 256 MB of memory
at 16:20:21 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
Header of the integral files:
NH3, planar
Integrals generated by seward 4.2.0 , Fri May 19 16:20:12 2006
Title:
NH3, planar
Cartesian coordinates:
-----------------------------------------
No. Label X Y Z
-----------------------------------------
1 N 0.00000 0.00000 0.00000
2 H1 2.00000 0.00000 0.00000
3 H2 -0.97604 1.69056 0.00000
4 H3 -0.97604 -1.69056 0.00000
-----------------------------------------
Nuclear repulsion energy = 11.551904
Orbital specifications :
Symmetry species 1 2
a' a"
Frozen orbitals 0 0
Occupied orbitals 4 1
Secondary orbitals 33 12
Del orbs due to Lin Dep 0 0
Total number of orbitals 37 13
Number of basis functions 37 13
Molecular charge 0.000
SCF Algorithm: Conventional SCF
Minimized density differences are used
Number of density matrices in core 40
Maximum number of NDDO SCF iterations 40
Maximum number of HF SCF iterations 40
Threshold for SCF energy change 0.10E-08
Threshold for density matrix 0.10E-03
Threshold for Fock matrix 0.15E-03
Threshold for linear dependence 0.10E-05
Threshold at which DIIS is turned on 0.15E+00
Threshold at which QNR/C2DIIS is turned on 0.15E+00
Threshold for Norm(delta) (QNR/C2DIIS) 0.20E-04
DIIS extrapolation of the SCF procedure
All orbitals punched on: SCFORB
Starting vectors from core diagonalization
SCF iterations: Energy and convergence statistics
Iter Tot. SCF One-electron Two-electron Energy Max Dij or Max Fij DNorm TNorm AccCon Time
Energy Energy Energy Change Delta Norm in Sec.
1 -46.20641083 -111.62867419 53.87035983 0.00E+00 0.36E+00* 0.11E+01* 0.12E+02 0.43E+02 NoneDa 0.
2 -46.06222307 -69.79562534 12.18149874 0.14E+00* 0.39E+00* 0.40E+00* 0.10E+03 0.29E+02 Damp 0.
3 -56.14314642 -100.32393421 32.62888426 -0.10E+02* 0.20E+00* 0.85E-01* 0.43E+01 0.33E+02 Damp 0.
4 -56.19135528 -98.14520877 30.40194996 -0.48E-01* 0.78E-01* 0.57E-01* 0.90E+00 0.32E+01 Damp 0.
5 -56.20049067 -99.38859049 31.63619629 -0.91E-02* 0.57E-01* 0.57E-01* 0.37E+00 0.12E+01 QNRc2D 0.
6 -56.20559055 -98.92176533 31.16427125 -0.51E-02* 0.16E-02* 0.12E-02* 0.30E-01 0.14E-01 QNRc2D 0.
7 -56.20559952 -98.92010323 31.16260018 -0.90E-05* 0.77E-03* 0.32E-03* 0.34E-02 0.21E-02 QNRc2D 0.
8 -56.20560056 -98.91996031 31.16245623 -0.10E-05* 0.18E-03* 0.49E-04 0.10E-02 0.71E-03 QNRc2D 0.
9 -56.20560059 -98.92015140 31.16264727 -0.37E-07* 0.33E-04* 0.88E-05 0.46E-03 0.83E-03 QNRc2D 0.
10 -56.20560060 -98.92016648 31.16266235 -0.11E-08* 0.29E-05 0.14E-05 0.70E-04 0.71E-04 QNRc2D 0.
11 -56.20560060 -98.92016777 31.16266364 -0.17E-10 0.46E-06 0.32E-06 0.10E-04 0.15E-04 QNRc2D 0.
Convergence after 11 Macro Iterations and 1 additional LS Iterations...
This job can be restarted with the RESTART option!
*****************************************************************************************************************************
* *
* SCF/KS-DFT Program, Final results *
* Molcas version 6.4 *
* *
* *
* Final Results *
* *
*****************************************************************************************************************************
Total SCF energy -56.2056005956
One-electron energy -98.9201677682
Two-electron energy 31.1626636429
Nuclear repulsion energy 11.5519035297
Kinetic energy (interpolated) 55.9226438580
Virial theorem 1.0050597883
Total spin, S(S+1) 0.0000000000
Total spin, S 0.0000000000
Max non-diagonal density matrix element 0.0000000000
Max non-diagonal Fock matrix element 0.0000003205
All orbitals with orbital energies smaller then E(LUMO)+0.5 are printed
Molecular orbitals:
-------------------
SCF orbitals
Molecular orbitals for symmetry species 1: a'
Orbital 1 2 3 4 5 6 7 8 9 10
Energy -15.5395 -1.1053 -0.6364 -0.6291 0.0420 0.0696 0.0696 0.2306 0.2770 0.2774
Occ. No. 2.0000 2.0000 2.0000 2.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
1 N 1s 0.9996 -0.0190 0.0000 0.0003 -0.1426 -0.0048 0.0000 0.4200 -0.0131 0.0000
2 N 1s -0.0005 0.8298 0.0000 0.0085 -1.2735 -0.0285 0.0000 2.8150 -0.0972 0.0000
3 N 1s -0.0017 0.0378 0.0000 -0.0010 -1.2204 -0.0225 0.0000 3.4832 -0.1177 0.0000
4 N 1s 0.0004 0.0027 0.0000 -0.0013 -0.4296 -0.0071 0.0000 1.1892 -0.0402 0.0000
5 N 2px 0.0000 -0.0084 0.0000 0.5936 -0.0357 1.3989 0.0000 0.0668 -2.2056 0.0000
6 N 2px 0.0000 -0.0003 0.0000 -0.0836 -0.0320 1.5876 0.0000 0.0804 -3.3105 0.0000
7 N 2px 0.0000 -0.0009 0.0000 -0.0005 -0.0003 0.1736 0.0000 -0.0085 -0.6868 0.0000
8 N 2py 0.0000 0.0000 0.5932 0.0000 0.0000 0.0000 1.4121 0.0000 0.0000 -2.2561
9 N 2py 0.0000 0.0000 -0.0861 0.0000 0.0000 0.0000 1.6018 0.0000 0.0000 -3.3862
10 N 2py 0.0000 0.0000 0.0020 0.0000 0.0000 0.0000 0.1719 0.0000 0.0000 -0.6904
11 N 3d2- 0.0000 0.0000 -0.0020 0.0000 0.0000 0.0000 -0.1530 0.0000 0.0000 0.2805
12 N 3d2- 0.0000 0.0000 0.0284 0.0000 0.0000 0.0000 -0.1506 0.0000 0.0000 0.3031
13 N 3d0 0.0003 -0.0135 0.0000 -0.0001 0.0039 -0.0037 0.0000 -0.1541 0.0066 0.0000
14 N 3d0 0.0001 0.0065 0.0000 -0.0001 0.0067 -0.0031 0.0000 -0.1518 0.0055 0.0000
15 N 3d2+ 0.0000 0.0004 0.0000 0.0029 -0.0068 0.1541 0.0000 0.0289 -0.2648 0.0000
16 N 3d2+ 0.0000 0.0011 0.0000 -0.0268 -0.0058 0.1516 0.0000 0.0236 -0.2863 0.0000
17 H1 1s 0.0011 0.1275 0.0000 0.4804 0.6162 -3.5815 0.0000 -1.1238 4.8127 0.0000
18 H1 1s 0.0001 -0.0466 0.0000 -0.0229 0.7143 -3.9222 0.0000 -1.1247 4.2343 0.0000
19 H1 1s -0.0001 0.0241 0.0000 0.0111 0.1556 -0.7033 0.0000 -0.1244 0.4427 0.0000
20 H1 2px -0.0003 -0.0071 0.0000 -0.0302 -0.0275 0.4291 0.0000 0.4366 -0.1992 0.0000
21 H1 2px 0.0000 0.0145 0.0000 0.0102 -0.0329 0.2951 0.0000 0.2896 -0.1180 0.0000
22 H1 2py 0.0000 0.0000 -0.0003 0.0000 0.0000 0.0000 -0.0382 0.0000 0.0000 -0.1776
23 H1 2py 0.0000 0.0000 -0.0115 0.0000 0.0000 0.0000 -0.0239 0.0000 0.0000 -0.1244
24 H2 1s 0.0011 0.1294 0.4118 -0.2341 0.5250 1.8006 -3.1837 -0.9159 -2.3375 4.3039
25 H2 1s 0.0002 -0.0548 -0.0243 0.0135 0.6421 1.9742 -3.4745 -0.9688 -2.0677 3.8139
26 H2 1s -0.0001 0.0260 0.0109 -0.0064 0.1511 0.3547 -0.6181 -0.1269 -0.2214 0.4080
27 H2 2px 0.0002 0.0033 0.0119 -0.0063 0.0054 0.0756 -0.2036 -0.1800 -0.1542 0.0148
28 H2 2px 0.0000 -0.0079 -0.0105 -0.0056 0.0123 0.0542 -0.1398 -0.1237 -0.1021 0.0038
29 H2 2py -0.0003 -0.0045 -0.0214 0.0119 -0.0108 -0.1963 0.3138 0.3018 -0.0131 -0.1918
30 H2 2py 0.0000 0.0146 0.0058 -0.0101 -0.0221 -0.1357 0.2174 0.2084 -0.0140 -0.1201
31 H3 1s 0.0011 0.1294 -0.4118 -0.2341 0.5250 1.8006 3.1837 -0.9159 -2.3375 -4.3039
32 H3 1s 0.0002 -0.0548 0.0243 0.0135 0.6421 1.9742 3.4745 -0.9688 -2.0677 -3.8139
33 H3 1s -0.0001 0.0260 -0.0109 -0.0064 0.1511 0.3547 0.6181 -0.1269 -0.2214 -0.4080
34 H3 2px 0.0002 0.0033 -0.0119 -0.0063 0.0054 0.0756 0.2036 -0.1800 -0.1542 -0.0148
35 H3 2px 0.0000 -0.0079 0.0105 -0.0056 0.0123 0.0542 0.1398 -0.1237 -0.1021 -0.0038
36 H3 2py 0.0003 0.0045 -0.0214 -0.0119 0.0108 0.1963 0.3138 -0.3018 0.0131 -0.1918
37 H3 2py 0.0000 -0.0146 0.0058 0.0101 0.0221 0.1357 0.2174 -0.2084 0.0140 -0.1201
Orbital 11 12 13
Energy 0.3117 0.3145 0.3839
Occ. No. 0.0000 0.0000 0.0000
1 N 1s 0.0354 0.0000 0.2351
2 N 1s 0.2289 0.0000 2.1586
3 N 1s 0.2379 0.0000 2.7369
4 N 1s 0.0799 0.0000 1.0680
5 N 2px -2.8898 0.0000 0.0987
6 N 2px -3.8815 0.0000 0.1172
7 N 2px -0.2759 0.0000 0.0037
8 N 2py 0.0000 2.9092 0.0000
9 N 2py 0.0000 3.8282 0.0000
10 N 2py 0.0000 0.2337 0.0000
11 N 3d2- 0.0000 -0.6484 0.0000
12 N 3d2- 0.0000 -0.5883 0.0000
13 N 3d0 0.0056 0.0000 0.2037
14 N 3d0 0.0037 0.0000 0.2047
15 N 3d2+ -0.6469 0.0000 0.0227
16 N 3d2+ -0.5889 0.0000 0.0200
17 H1 1s 6.4217 0.0000 -1.4059
18 H1 1s 5.4783 0.0000 -0.8399
19 H1 1s 0.4115 0.0000 0.0412
20 H1 2px -1.5238 0.0000 -0.0773
21 H1 2px -0.9483 0.0000 -0.0547
22 H1 2py 0.0000 -0.1558 0.0000
23 H1 2py 0.0000 -0.0957 0.0000
24 H2 1s -3.3449 -5.7206 -1.1250
25 H2 1s -2.8329 -4.8038 -0.6302
26 H2 1s -0.2109 -0.3344 0.0451
27 H2 2px -0.2641 -0.7409 0.0681
28 H2 2px -0.1663 -0.4608 0.0438
29 H2 2py 0.7242 1.1239 -0.1490
30 H2 2py 0.4522 0.6997 -0.0982
31 H3 1s -3.3449 5.7206 -1.1250
32 H3 1s -2.8329 4.8038 -0.6302
33 H3 1s -0.2109 0.3344 0.0451
34 H3 2px -0.2641 0.7409 0.0681
35 H3 2px -0.1663 0.4608 0.0438
36 H3 2py -0.7242 1.1239 0.1490
37 H3 2py -0.4522 0.6997 0.0982
Molecular orbitals for symmetry species 2: a"
Orbital 1 2 3 4
Energy -0.3871 0.1675 0.4139 0.4165
Occ. No. 2.0000 0.0000 0.0000 0.0000
1 N 2pz 0.9202 0.4496 0.0137 0.0000
2 N 2pz 0.0267 1.3848 0.0177 0.0000
3 N 2pz -0.0254 0.4563 0.0050 0.0000
4 N 3d1- 0.0000 0.0000 0.0000 0.1682
5 N 3d1- 0.0000 0.0000 0.0000 0.1894
6 N 3d1+ 0.0000 -0.0056 -0.1621 0.0000
7 N 3d1+ 0.0004 -0.0064 -0.1828 0.0000
8 H1 2pz 0.0490 -0.2443 -0.6828 0.0000
9 H1 2pz 0.0112 -0.1929 -0.5322 0.0000
10 H2 2pz 0.0504 -0.2613 0.3253 0.5811
11 H2 2pz 0.0113 -0.2057 0.2535 0.4531
12 H3 2pz 0.0504 -0.2613 0.3253 -0.5811
13 H3 2pz 0.0113 -0.2057 0.2535 -0.4531
Mulliken charges per centre and basis function type
N H1 H2 H3
1s 3.6299 0.7332 0.7193 0.7193
2px 1.0978 0.0094 -0.0023 -0.0023
2py 1.0994 -0.0066 0.0033 0.0033
2pz 1.8361 0.0528 0.0556 0.0556
3d0 0.0026 0.0000 0.0000 0.0000
3d2+ -0.0030 0.0000 0.0000 0.0000
3d2- -0.0033 0.0000 0.0000 0.0000
3d1- 0.0000 0.0000 0.0000 0.0000
3d1+ 0.0000 0.0000 0.0000 0.0000
Total 7.6594 0.7888 0.7759 0.7759
N-E -0.6594 0.2112 0.2241 0.2241
Total electronic charge= 10.000000
Total charge= 0.000000
LoProp Charges per center
N H1 H2 H3
Nuclear 7.0000 1.0000 1.0000 1.0000
Electronic -7.7547 -0.7499 -0.7477 -0.7477
Total -0.7547 0.2501 0.2523 0.2523
Dipole Moment (Debye):
Origin of the operator (Ang)= 0.0000 0.0000 0.0000
X= 0.0188 Y= 0.0000 Z= 0.0000 Total= 0.0188
Quadrupole Moment (Debye*Ang):
Origin of the operator (Ang)= 0.0054 0.0000 0.0000
XX= -5.6471 XY= 0.0000 XZ= 0.0000 YY= -5.7241
YZ= 0.0000 ZZ= -10.1563
In traceless form (Debye*Ang)
XX= 2.2931 XY= 0.0000 XZ= 0.0000 YY= 2.1776
YZ= 0.0000 ZZ= -4.4707
--- Stop Module: scf at Fri May 19 16:20:25 BST 2006 /rc= 0 ---
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module ALASKA with 256 MB of memory
at 16:20:29 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
Threshold for contributions to the gradient: .100E-06
Wavefunction type: RHF-SCF
**************************************************
* *
* Molecular gradients *
* *
**************************************************
Irreducible representation: a'
N x -0.1765090E-01
N y -0.6720023E-12
H1 x 0.6183894E-01
H1 y 0.4749777E-13
H2 x -0.2209402E-01
H2 y 0.3738753E-01
H3 x -0.2209402E-01
H3 y -0.3738753E-01
--- Stop Module: alaska at Fri May 19 16:20:36 BST 2006 /rc= 0 ---
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module SLAPAF with 256 MB of memory
at 16:20:38 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
Max iterations: 20
Convergence test a la Schlegel.
Convergence criterion on gradient/para.<=: 0.3E-03
Convergence criterion on step/parameter<=: 0.3E-03
Convergence criterion on energy change <=: 0.1E-05
Max norm of step: 0.30E+00
Line search is performed
-Optimization for minimum.
Optimization method: RS-RFO.
-Initial Hessian guessed by Hessian Model Function (HMF).
HMF augmented with weak interactions.
-Hessian update method: Broyden-Fletcher-Goldfarb-Shanno
Max number of points in Hessian update: 5
-Relaxation will be done in nonredundant internal coordinates, based on
force constant weighted redundant internal coordinates.
*****************************************************************************************************************
********************************** Energy Statistics for Geometry Optimization **********************************
*****************************************************************************************************************
Energy Grad Grad Step Estimated Geom Hessian
Iter Energy Change Norm Max Element Max Element Final Energy Update Update Index
1 -56.20560060 0.00000000 0.088924-0.085958 nrc001 -0.151844 nrc001 -56.21235586 RS-RFO None 0
Cartesian Displacements Gradient in internals
Value Threshold Converged? Value Threshold Converged?
+----------------------------------+----------------------------------+
RMS + 0.7711E-01 0.1200E-02 No + 0.5134E-01 0.3000E-03 No +
+----------------------------------+----------------------------------+
Max + 0.1054E+00 0.1800E-02 No + 0.8596E-01 0.4500E-03 No +
+----------------------------------+----------------------------------+
Convergence not reached yet!
*****************************************************************************************************************
*****************************************************************************************************************
Geometrical information of the new structure
Nuclear coordinates for the next iteration / Bohr, Angstrom
ATOM X Y Z X Y Z
N 0.0085227166 0.0000000000 0.0000000000 0.0045100274 0.0000000000 0.0000000000
H1 1.8945668735 0.0000000000 0.0000000000 1.0025616138 0.0000000000 0.0000000000
H2 -0.9275887906 1.6277132219 0.0000000000 -0.4908588490 0.8613487427 0.0000000000
H3 -0.9275887906 -1.6277132219 0.0000000000 -0.4908588490 -0.8613487427 0.0000000000
***************************************
**** InterNuclear Distances / Bohr ****
***************************************
1 N 2 H1 3 H2 4 H3
1 N 0.000000
2 H1 1.886044 0.000000
3 H2 1.877699 3.257915 0.000000
4 H3 1.877699 3.257915 3.255426 0.000000
*******************************************
**** InterNuclear Distances / Angstrom ****
*******************************************
1 N 2 H1 3 H2 4 H3
1 N 0.000000
2 H1 0.998052 0.000000
3 H2 0.993636 1.724015 0.000000
4 H3 0.993636 1.724015 1.722697 0.000000
**************************************
**** Valence Bond Angles / Degree ****
**************************************
Atom centers Phi
2 H1 1 N 3 H2 119.90
2 H1 1 N 4 H3 119.90
3 H2 1 N 4 H3 120.19
***************************************************
*** Radius of hypersphere relative the starting ***
*** structure / au*amu**(1/2)/amu(1/2) ***
***************************************************
0.0383
--- Stop Module: slapaf at Fri May 19 16:20:40 BST 2006 /rc= 1 ---
--- Stop Module: auto at Fri May 19 16:20:40 BST 2006 /rc=1 ---
Output file (gzipped) ex1.out can be downloaded here. MOLDEN file (gzipped) ex1.scf.molden can be downloaded here. MOLDEN file (gzipped) ex1.geo.molden can be downloaded here. |
| Example 2. CASPT2 Calculation of Water
From the program modules dependencies flow chart, one can see which program modules are required in order to carry out an CASPT2 calculation. In this case, the program modules SEWARD, SCF, RASSCF are required prior to CASPT2. The ORDINT file from the SEWARD module and the JOBIPH file from the RASSCF module are the required input files for the CASPT2 module. The orbitals are saved in the PT2ORB file. The new PM-CASSCF wave function generated in a MS-CASPT2 calculation is saved in the JOBMIX file. In this example, the Multistate option is used, therefore the program will perform one CASPT2 calculation for each one of the selected roots, and finally the complete effective Hamiltonian containing the selected states will be solved to obtain the final MS-CASPT2 energies and PM-CASSCF (Perturbation Modified-CASSCF) wavefunctions. |
Input |
ex2.input
&SEWARD &END Title Water - The integrals of water are calculated using C2v symmetry Symmetry (=C2v as O is at the origin of the xy plane) XY Y *Test Comments can be inserted by starting the line with the symbol * Basis Set O.ano-s.Pierloot.10s6p3d.2s1p0d. *O.ano-s.Pierloot.10s6p3d.3s2p1d. *O.ano-s.Pierloot.10s6p3d.4s3p2d. O1 0.0 0.0 0.0 End of Basis Set Basis Set H.ano-s.Pierloot.7s3p.1s0p. *H.ano-s.Pierloot.7s3p.2s1p. *H.ano-s.Pierloot.7s3p.3s2p. H1 1.4 0.0 1.4 End of Basis Set End of Input &SCF &END Title Water - A Tutorial The SCF energy of water is calculated using C2v symmetry Occupied Number of occupied orbitals in each of the irreducible representations 3 1 0 1 OccNumbers Occupation number in each orbitals 2.0 2.0 2.0 2.0 2.0 IVO IVO keyword prepares the virtual orbitals for MCSCF End of Input &RASSCF &END Title The CASSCF energy of water is calculated using C2v symmetry. 2 3B2 state. Inactive Number of inactive orbitals in each symmetry 1 0 0 0 Ras2 RAS2 orbitals: all possible occupations are allowed in this example 3 2 0 1 nActEl Total no. of active electrons [1] This specifies the CI root(s) and the dimension of the starting CI matrix used in the CI Davidson procedure. This input makes it possible to perform orbital optimization for the average energy of a number of states. The first line of input gives two or three numbers, specifying the number of roots used in the average calculation (NROOTS), the dimension of the small CI matrix in the Davidson procedure (LROOTS), and possibly a non-zero integer IALL. If IALL.ne.1 or there is no IALL, the second line gives the index of the states over which the average is taken (NROOTS numbers, IROOT). Note that the size of the CI matrix, LROOTS, must be at least as large as the highest root, IROOT. If, and only if, NROOTS1 a third line follows, specifying the weights of the different states in the average energy. Example: If IALL=1 has been specified, no more lines are read. A state average calculation will be performed over the NROOTS lowest states with equal weights. [2] Input molecular orbitals are read from a formatted file with FORTRAN file name INPORB. Note, the keywords Lumorb, Core, and Jobiph are mutually exclusive. [3] This keyword is used to specify the number of frozen orbitals, i.e. the orbitals that are not correlated in the calculation. The next line contain the number of frozen orbitals per symmetry. The default is to freeze those that were frozen in the RASSCF calculation. The frozen orbitals are always the first ones in each symmetry. [4] The maximum allowed number of iterations in a procedure for solving a system of linear equations using a conjugate gradient method, a gradient norm is reported. Input file (gzipped) auto.input can be downloaded here. |
Output |
ex2.out
^^^^^ M O L C A S
^^^^^^^ version 6.4 patchlevel 099
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Copyright, all rights, reserved:
Permission is hereby granted to use
but not to reproduce or distribute any part of this
program. The use is restricted to research purposes only.
Lund University Sweden, 2006.
For the author list and the recommended citation consult section 1.5 of the MOLCAS user's guide.
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module SEWARD with 256 MB of memory
at 15:21:36 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
SEWARD will generate:
Multipole Moment integrals up to order 2
Kinetic Energy integrals
Nuclear Attraction integrals
One-Electron Hamiltonian integrals
Two-Electron Repulsion integrals
Title:
Water - The integrals of water are calculated using C2v symmetry
--- Group Generators ---
Rotation around the z-axis
Reflection in the xz-plane
Integrals are discarded if absolute value <: 0.10E-13
Integral cutoff threshold is set to <: 0.10E-15
Character Table for C2v
E C2(z) s(xz) s(yz)
a1 1 1 1 1 z
b1 1 -1 1 -1 x, xz, Ry
a2 1 1 -1 -1 xy, Rz, I
b2 1 -1 -1 1 y, yz, Rx
Unitary symmetry adaptation
Basis set label:O.ANO-S.PIERLOOT.10S6P3D.2S1P0D.
Valence basis set:
==================
Associated Effective Charge 8.000000 au
Associated Actual Charge 8.000000 au
Shell nPrim nBasis Cartesian Spherical Contaminant
s 10 2 X
p 6 1 X
Basis set label:H.ANO-S.PIERLOOT.7S3P.1S0P.
Valence basis set:
==================
Associated Effective Charge 1.000000 au
Associated Actual Charge 1.000000 au
Shell nPrim nBasis Cartesian Spherical Contaminant
s 7 1 X
************************************************
**** Cartesian Coordinates / Bohr, Angstrom ****
************************************************
Center Label x y z x y z
1 O1 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
2 H1 1.400000 0.000000 1.400000 0.740848 0.000000 0.740848
3 H1 -1.400000 0.000000 1.400000 -0.740848 0.000000 0.740848
***************************************
**** InterNuclear Distances / Bohr ****
***************************************
1 O1 2 H1 3 H1
1 O1 0.000000
2 H1 1.979899 0.000000
3 H1 1.979899 2.800000 0.000000
*******************************************
**** InterNuclear Distances / Angstrom ****
*******************************************
1 O1 2 H1 3 H1
1 O1 0.000000
2 H1 1.047717 0.000000
3 H1 1.047717 1.481696 0.000000
**************************************
**** Valence Bond Angles / Degree ****
**************************************
Atom centers Phi
2 H1 1 O1 3 H1 90.00
1 O1 2 H1 3 H1 45.00
1 O1 3 H1 2 H1 45.00
Basis set specifications :
Symmetry species a1 b1 a2 b2
Basis functions 4 2 0 1
Nuclear Potential Energy 8.43836321 au
--- Stop Module: seward at Fri May 19 15:21:59 BST 2006 /rc= 0 ---
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module SCF with 256 MB of memory
at 15:22:11 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
Header of the integral files:
Water - The integrals of water are calculated using C2v symmetry
Integrals generated by seward 4.2.0 , Fri May 19 15:21:50 2006
Title:
Water - A Tutorial
THE SCF ENERGY OF WATER IS CALCULATED USING C2V SYMMETRY
Cartesian coordinates:
-----------------------------------------
No. Label X Y Z
-----------------------------------------
1 O1 0.00000 0.00000 0.00000
2 H1 1.40000 0.00000 1.40000
3 H1 -1.40000 0.00000 1.40000
-----------------------------------------
Nuclear repulsion energy = 8.438363
Orbital specifications :
Symmetry species 1 2 3 4
a1 b1 a2 b2
Frozen orbitals 0 0 0 0
Occupied orbitals 3 1 0 1
Secondary orbitals 1 1 0 0
Del orbs due to Lin Dep 0 0 0 0
Total number of orbitals 4 2 0 1
Number of basis functions 4 2 0 1
Molecular charge 0.000
SCF Algorithm: Conventional SCF
Minimized density differences are used
Number of density matrices in core 100
Maximum number of NDDO SCF iterations 100
Maximum number of HF SCF iterations 100
Threshold for SCF energy change 0.10E-08
Threshold for density matrix 0.10E-03
Threshold for Fock matrix 0.15E-03
Threshold for linear dependence 0.10E-05
Threshold at which DIIS is turned on 0.15E+00
Threshold at which QNR/C2DIIS is turned on 0.15E+00
Threshold for Norm(delta) (QNR/C2DIIS) 0.20E-04
DIIS extrapolation of the SCF procedure
Improved virtual orbitals.
All orbitals punched on: SCFORB
Starting vectors from core diagonalization
SCF iterations: Energy and convergence statistics
Iter Tot. SCF One-electron Two-electron Energy Max Dij or Max Fij DNorm TNorm AccCon Time
Energy Energy Energy Change Delta Norm in Sec.
1 -74.28509350 -126.92217783 44.19872111 0.00E+00 0.10E+01* 0.47E+00* 0.59E+01 0.22E+02 NoneDa 0.
2 -75.85356423 -119.72498564 35.43305819 -0.16E+01* 0.29E+00* 0.16E+00* 0.41E+01 0.11E+02 Damp 0.
3 -75.92502806 -121.64052958 37.27713831 -0.71E-01* 0.54E-01* 0.36E-01* 0.73E+00 0.80E+00 Damp 0.
4 -75.92806378 -121.28246529 36.91603829 -0.30E-02* 0.90E-02* 0.36E-01* 0.92E-01 0.98E-01 QNRc2D 0.
5 -75.92822494 -121.34726866 36.98068051 -0.16E-03* 0.28E-02* 0.19E-02* 0.10E-01 0.12E-02 QNRc2D 0.
6 -75.92824407 -121.34113437 36.97452709 -0.19E-04* 0.14E-02* 0.81E-03* 0.55E-03 0.76E-03 QNRc2D 0.
7 -75.92824652 -121.33768877 36.97107904 -0.24E-05* 0.16E-03* 0.14E-03 0.43E-04 0.12E-04 QNRc2D 0.
8 -75.92824657 -121.33781849 36.97120871 -0.50E-07* 0.20E-06 0.31E-06 0.13E-05 0.94E-06 QNRc2D 0.
9 -75.92824657 -121.33781790 36.97120812 -0.27E-12 0.38E-06 0.20E-06 0.62E-08 0.14E-08 QNRc2D 0.
Convergence after 9 Macro Iterations and 0 additional LS Iterations...
This job can be restarted with the RESTART option!
*****************************************************************************************************************************
* *
* SCF/KS-DFT Program, Final results *
* Molcas version 6.4 *
* *
* *
* Final Results *
* *
*****************************************************************************************************************************
Total SCF energy -75.9282465666
One-electron energy -121.3378178998
Two-electron energy 36.9712081197
Nuclear repulsion energy 8.4383632136
Kinetic energy (interpolated) 76.1227519565
Virial theorem 0.9974448455
Total spin, S(S+1) 0.0000000000
Total spin, S 0.0000000000
Max non-diagonal density matrix element 0.0000000000
Max non-diagonal Fock matrix element 0.0000002046
All orbitals with orbital energies smaller then E(LUMO)+0.5 are printed
Molecular orbitals:
-------------------
SCF orbitals + arbitrary occupations
Molecular orbitals for symmetry species 1: a1
Orbital 1 2 3 4
Energy -20.5611 -1.3467 -0.5957 0.0000
Occ. No. 2.0000 2.0000 2.0000 0.0000
1 O1 1s 1.0000 -0.0131 -0.0264 -0.0797
2 O1 1s 0.0011 0.8608 -0.4646 -0.7760
3 O1 2pz 0.0017 0.1392 0.7809 -0.7749
4 H1 1s -0.0006 0.1647 0.3429 1.0880
Molecular orbitals for symmetry species 2: b1
Orbital 1 2
Energy -0.6514 0.0000
Occ. No. 2.0000 0.0000
1 O1 2px 0.6803 -0.9493
2 H1 1s 0.5732 1.3330
Molecular orbitals for symmetry species 4: b2
Orbital 1
Energy -0.5428
Occ. No. 2.0000
1 O1 2py 1.0000
Mulliken charges per centre and basis function type
O1 H1
1s 3.8912 0.6793
2pz 1.5002 0.0000
2px 1.2500 0.0000
2py 2.0000 0.0000
Total 8.6414 0.6793
N-E -0.6414 0.3207
Total electronic charge= 10.000000
Total charge= 0.000000
LoProp Charges per center
O1 H1
Nuclear 8.0000 1.0000
Electronic -8.4992 -0.7504
Total -0.4992 0.2496
Dipole Moment (Debye):
Origin of the operator (Ang)= 0.0000 0.0000 0.0000
X= 0.0000 Y= 0.0000 Z= 2.2884 Total= 2.2884
Quadrupole Moment (Debye*Ang):
Origin of the operator (Ang)= 0.0000 0.0000 0.2961
XX= -6.1879 XY= 0.0000 XZ= 0.0000 YY= -8.1722
YZ= 0.0000 ZZ= -6.3612
In traceless form (Debye*Ang)
XX= 1.0788 XY= 0.0000 XZ= 0.0000 YY= -1.8976
YZ= 0.0000 ZZ= 0.8189
--- Stop Module: scf at Fri May 19 15:22:20 BST 2006 /rc= 0 ---
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module RASSCF with 256 MB of memory
at 15:22:31 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
Orbital specification was read from input.
Orbitals will be read from INPORB.
**************************************************************************************************************************
* *
* Project: *
* The CASSCF energy of water is calculated using C2v symmetry. 2 3B2 state *
* *
**************************************************************************************************************************
Header of the ONEINT file:
--------------------------
Water - The integrals of water are calculated using C2v symmetry
Integrals generated by seward 4.2.0 , Fri May 19 15:21:50 2006
OrdInt status: non-squared
Cartesian coordinates:
-----------------------------------------
No. Label X Y Z
-----------------------------------------
1 O1 0.00000 0.00000 0.00000
2 H1 1.40000 0.00000 1.40000
3 H1 -1.40000 0.00000 1.40000
-----------------------------------------
Nuclear repulsion energy = 8.438363
Wave function specifications:
-----------------------------
Number of closed shell electrons 0
Number of electrons in active shells 8
Max number of holes in RAS1 space 0
Max nr of electrons in RAS3 space 0
Number of inactive orbitals 0
Number of active orbitals 6
Number of secondary orbitals 0
Spin quantum number 1.0
State symmetry 2
Orbital specifications:
-----------------------
Symmetry species 1 2 3 4
a1 b1 a2 b2
Frozen orbitals 0 0 0 0
Inactive orbitals 1 0 0 0
Active orbitals 3 2 0 1
RAS1 orbitals 0 0 0 0
RAS2 orbitals 3 2 0 1
RAS3 orbitals 0 0 0 0
Secondary orbitals 0 0 0 0
Deleted orbitals 0 0 0 0
Number of basis functions 4 2 0 1
CI expansion specifications:
----------------------------
Number of configuration state fnc. 30
Number of determinants 32
Number of root(s) required 1
CI root used 2
highest root include in the CI 2
max. size of the explicit Hamiltonian 30
Optimization specifications:
----------------------------
RASSCF algorithm: Conventional
Maximum number of macro iterations 200
Maximum number of CI iterations 200
Maximum number of SX iterations 100
Threshold for RASSCF energy 0.100E-07
Threshold for max MO rotation 0.100E-03
Threshold for max BLB element 0.100E-03
Level shift parameter 0.100E+01
Make Quasi-Newton update
Input orbitals:
---------------
The MO-coefficients are taken from the file INPORB
title: SCF orbitals + arbitrary occupations
************************************************************************************************************************
* *
* Wave function control section *
* *
************************************************************************************************************************
RASSCF iterations: Energy and convergence statistics
----------------------------------------------------
Iter CI SX CI RASSCF Energy max BLB max BLB max ROT Level Ln srch Step QN Time(min)
iter iter root energy change element value param shift minimum type update CPU
1 1 4 2 -75.44396426 0.00E+00 1 4 1 -0.18E-01 -0.68E-02 0.00 0.00 SX NO 0.00
2 1 4 2 -75.44398965 -0.25E-04 1 4 1 -0.77E-03 0.58E-03 0.00 1.07 QN YES 0.00
3 1 3 2 -75.44398976 -0.11E-06 1 4 1 0.14E-04 0.16E-05 0.00 0.99 QN YES 0.00
4 1 2 2 -75.44398976 -0.77E-11 1 3 1 -0.32E-06 -0.50E-06 0.00 1.01 QN YES 0.00
Convergence after 4 iterations
5 1 2 2 -75.44398976 -0.99E-13 1 3 1 -0.24E-06 -0.50E-06 0.00 1.01 QN YES 0.00
************************************************************************************************************************
Wave function printout:
occupation of active orbitals, and spin coupling of open shells (u,d: Spin up or down)
************************************************************************************************************************
printout of CI-coefficients larger than 0.05 for root 1
energy= -75.519542
conf/sym 111 22 4 Coeff Weight
3 22u u0 2 -0.74130 0.54953
7 2u2 u0 2 -0.10071 0.01014
8 2u2 0u 2 0.07545 0.00569
13 2u0 2u 2 -0.63081 0.39792
14 2u0 u2 2 -0.05508 0.00303
15 u20 2u 2 0.13974 0.01953
18 20u u2 2 0.06679 0.00446
printout of CI-coefficients larger than 0.05 for root 2
energy= -75.443990
conf/sym 111 22 4 Coeff Weight
3 22u u0 2 0.64031 0.40999
4 22u 0u 2 0.07674 0.00589
13 2u0 2u 2 -0.75133 0.56450
14 2u0 u2 2 0.06193 0.00384
19 udu 2u 2 0.06489 0.00421
Natural orbitals and occupation numbers for root 1
sym 1: 1.995347 1.552927 0.588774
sym 2: 1.415506 0.448672
sym 4: 1.998774
Natural orbitals and occupation numbers for root 2
sym 1: 1.986957 1.416217 0.437262
sym 2: 1.567238 0.594658
sym 4: 1.997668
************************************************************************************************************************
* *
* Final results *
* *
************************************************************************************************************************
Wave function specifications:
-----------------------------
Number of closed shell electrons 0
Number of electrons in active shells 8
Max number of holes in RAS1 space 0
Max nr of electrons in RAS3 space 0
Number of inactive orbitals 0
Number of active orbitals 6
Number of secondary orbitals 0
Spin quantum number 1.0
State symmetry 2
Orbital specifications:
-----------------------
Symmetry species 1 2 3 4
a1 b1 a2 b2
Frozen orbitals 0 0 0 0
Inactive orbitals 1 0 0 0
Active orbitals 3 2 0 1
RAS1 orbitals 0 0 0 0
RAS2 orbitals 3 2 0 1
RAS3 orbitals 0 0 0 0
Secondary orbitals 0 0 0 0
Deleted orbitals 0 0 0 0
Number of basis functions 4 2 0 1
CI expansion specifications:
----------------------------
Number of configuration state fnc. 30
Number of determinants 32
Number of root(s) required 1
CI root used 2
highest root include in the CI 2
Final optimization conditions:
------------------------------
Average CI energy -75.44398976
RASSCF energy -75.44398976
Super-CI energy 0.00000000
RASSCF energy change 0.00000000
Max change in MO coefficients -0.501E-06
Max non-diagonal density matrix element -0.501E-06
Maximum BLB matrix element -0.244E-06
(orbital pair 1, 3 in symmetry 1)
Final state energy(ies):
------------------------
root number 1 E = -75.51954156 a.u.
root number 2 E = -75.44398976 a.u.
Molecular orbitals:
-------------------
Pseudonatural active orbitals and approximate occupation numbers
Molecular orbitals for symmetry species 1: a1
Orbital 1 2 3 4
Energy -20.5673 0.0000 0.0000 0.0000
Occ. No. 2.0000 1.9870 1.4162 0.4373
1 O1 1s 1.0001 -0.0084 -0.0194 -0.0818
2 O1 1s -0.0054 0.8009 -0.5169 -0.8065
3 O1 2pz -0.0004 0.2412 0.8066 -0.7218
4 H1 1s -0.0014 0.1991 0.2471 1.1080
Molecular orbitals for symmetry species 2: b1
Orbital 1 2
Energy 0.0000 0.0000
Occ. No. 1.5672 0.5947
1 O1 2px 0.7344 -0.9081
2 H1 1s 0.4946 1.3641
Molecular orbitals for symmetry species 4: b2
Orbital 1
Energy 0.0000
Occ. No. 1.9977
1 O1 2py 1.0000
Mulliken population Analysis for root number: 1
-----------------------------------------------
Mulliken charges per centre and basis function type
O1 H1
1s 3.9194 0.8602
2pz 1.2971 0.0000
2px 1.0643 0.0000
2py 1.9988 0.0000
Total 8.2796 0.8602
N-E -0.2796 0.1398
Total electronic charge= 10.000000
Total charge= 0.000000
Expectation values of various properties for root number: 1
---------------------------------------------------------
Dipole Moment (Debye):
Origin of the operator (Ang)= 0.0000 0.0000 0.0000
X= 0.0000 Y= 0.0000 Z= 0.7969 Total= 0.7969
Quadrupole Moment (Debye*Ang):
Origin of the operator (Ang)= 0.0000 0.0000 0.2961
XX= -7.1573 XY= 0.0000 XZ= 0.0000 YY= -8.2315
YZ= 0.0000 ZZ= -7.3255
In traceless form (Debye*Ang)
XX= 0.6212 XY= 0.0000 XZ= 0.0000 YY= -0.9902
YZ= 0.0000 ZZ= 0.3689
Mulliken spin population Analysis for root number: 1
---------------------------------------------------
Mulliken charges per centre and basis function type
O1 H1
1s 0.0492 0.4359
2pz 0.5184 0.0000
2px 0.5605 0.0000
2py 0.0000 0.0000
Total 1.1281 0.4359
Total electronic spin= 2.000000
LoProp population Analysis for root number: 1
-----------------------------------------------
LoProp Charges per center
O1 H1
Nuclear 8.0000 1.0000
Electronic -8.1640 -0.9180
Total -0.1640 0.0820
Mulliken population Analysis for root number: 2
-----------------------------------------------
Mulliken charges per centre and basis function type
O1 H1
1s 3.7723 0.8437
2pz 1.2764 0.0000
2px 1.2662 0.0000
2py 1.9977 0.0000
Total 8.3125 0.8437
N-E -0.3125 0.1563
Total electronic charge= 10.000000
Total charge= 0.000000
Expectation values of various properties for root number: 2
---------------------------------------------------------
Dipole Moment (Debye):
Origin of the operator (Ang)= 0.0000 0.0000 0.0000
X= 0.0000 Y= 0.0000 Z= 0.7345 Total= 0.7345
Quadrupole Moment (Debye*Ang):
Origin of the operator (Ang)= 0.0000 0.0000 0.2961
XX= -7.1645 XY= 0.0000 XZ= 0.0000 YY= -8.1337
YZ= 0.0000 ZZ= -6.9557
In traceless form (Debye*Ang)
XX= 0.3802 XY= 0.0000 XZ= 0.0000 YY= -1.0736
YZ= 0.0000 ZZ= 0.6934
Mulliken spin population Analysis for root number: 2
---------------------------------------------------
Mulliken charges per centre and basis function type
O1 H1
1s 0.0399 0.6025
2pz 0.4053 0.0000
2px 0.3499 0.0000
2py 0.0000 0.0000
Total 0.7951 0.6025
Total electronic spin= 2.000000
LoProp population Analysis for root number: 2
-----------------------------------------------
LoProp Charges per center
O1 H1
Nuclear 8.0000 1.0000
Electronic -8.1673 -0.9164
Total -0.1673 0.0836
Input file to MOLDEN was generated!
Average orbitals are written to the RASORB file
Timings
-------
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
time fraction
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
1) Input section : 0.01 0.04
- Input processing : 0.01 0.04
- Create GUGA tables : 0.00 0.00
- Create determinant tables : 0.00 0.00
2) Wave function optimization : 0.10 0.37
- transformation section : 0.01 0.04
. AO=>MO integral transformation : 0.00 0.00
. Fock-matrix generation : 0.00 0.00
- CI optimization : 0.05 0.19
. construct Hdiag : 0.00 0.00
. construct Hsel : 0.00 0.00
. Davidson diagonalization : 0.00 0.00
.. sigma vector generation : 0.00 0.00
.. HCSCE : 0.00 0.00
.. page_in/page_out : 0.00 0.00
. density matrix generation : 0.03 0.11
- orbital optimization : 0.04 0.15
3) Output section : 0.16 0.59
- Create/update the file RELAX : 0.01 0.04
- Create/update the file RUNFILE : 0.00 0.00
- Create/update the file JOBIPH : 0.15 0.56
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
Total : 0.27 1.00
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
--- Stop Module: rasscf at Fri May 19 15:22:48 BST 2006 /rc= 0 ---
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
MOLCAS executing module CASPT2 with 256 MB of memory
at 15:22:55 Fri May 19 2006
()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()()
WARNING!
Default frozen orbitals as max of non valence orbitals and orbitals frozen in the CASSCF is overwritten by user input.
Default values: 1 0 0 0
**************************************************************************************************************************
* *
* Project: *
* ( No title was given. ) *
* *
**************************************************************************************************************************
Wave function specifications:
-----------------------------
Number of closed shell electrons 0
Number of electrons in active shells 8
Max number of holes in RAS1 space 0
Max number of electrons in RAS3 space 0
Number of inactive orbitals 0
Number of active orbitals 6
Number of secondary orbitals 0
Spin quantum number 1.0
State symmetry 2
Number of configuration state fnc. 30
Number of root(s) available 1
A file JOBMIX will be created.
This is a CASSCF reference function
Orbital specifications:
-----------------------
Symmetry species 1 2 3 4
a1 b1 a2 b2
Frozen orbitals 1 0 0 0
Inactive orbitals 0 0 0 0
Active orbitals 3 2 0 1
Secondary orbitals 0 0 0 0
Deleted orbitals 0 0 0 0
Number of basis functions 4 2 0 1
Type of Fock operator to use: STANDARD
Type of HZERO operator to use: STANDARD IPEA
The CANONICAL keyword was not used in the RASSCF program.
Therefore, input orbitals should be transformed.
The input orbitals and the CI vector will be transformed.
--------------------------------------------------------------------------------
Estimated memory requirements:
POLY3 : 116754
MKRHS : 100018
SIGMA : 108016
DIADNS: 0
PRPCTL: 108075
Available workspace: 33549532
********************************************************************************
Single-state initialization phase begins for state 1
--------------------------------------------------------------------------------
The internal wave function representation has been changed to use quasi-canonical orbitals:
those which diagonalize the Fock matrix within inactive-inactive,
active-active and virtual-virtual submatrices.
--------------------------------------------------------------------------------
Single-state initialization phase finished.
********************************************************************************
CASPT2 EQUATION SOLUTION
--------------------------------------------------------------------------------
Total nr of CASPT2 parameters:
Before reduction: 0
After reduction: 0
------------------------------------------------------------------------------------------------
FINAL CASPT2 RESULT:
Correlation energy /Case, /Symm, and sums:
VJTU 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
VJTIP 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
VJTIM 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
ATVX 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
AIVX 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
VJAIP 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
VJAIM 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
BVATP 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
BVATM 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
BJATP 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
BJATM 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
BJAIP 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
BJAIM 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
Summed: 0.00000000 0.00000000 0.00000000 0.00000000 0.00000000
Reference energy: -75.5195415554
E2 (Non-variational): 0.0000000000
E2 (Variational): 0.0000000000
Total energy: -75.5195415554
Residual norm: 0.0000000000
Reference weight: 1.00000
Contributions to the CASPT2 correlation energy
Active & Virtual Only: 0.0000000000
One Inactive Excited: 0.0000000000
Two Inactive Excited: 0.0000000000
----------------------------------------------------------------------------------------------------
Report on small energy denominators, large coefficients, and large energy contributions.
The ACTIVE-MIX index denotes linear combinations which gives ON expansion functions
and makes H0 diagonal within type.
DENOMINATOR: The (H0_ii - E0) value from the above-mentioned diagonal approximation.
RHS VALUE : Right-Hand Side of CASPT2 Eqs.
COEFFICIENT: Multiplies each of the above ON terms in the first-order wave function.
Thresholds used:
Denominators: 0.3000
Coefficients: 0.0250
Energy contributions: 0.0050
CASE SYMM ACTIVE-MIX NON-ACTIVE INDICES DENOMINATOR RHS VALUE COEFFICIENT CONTRIBUTION
********************************************************************************
CASPT2 PROPERTY SECTION
--------------------------------------------------------------------------------
Mulliken population Analysis:
-----------------------------
Mulliken charges per centre and basis function type
O1 H1
1s 3.9194 0.8602
2pz 1.2971 0.0000
2px 1.0643 0.0000
2py 1.9988 0.0000
Total 8.2796 0.8602
N-E -0.2796 0.1398
Total electronic charge= 10.000000
Total charge= 0.000000
Expectation values of various properties:
-----------------------------------------
Dipole Moment (Debye):
Origin of the operator (Ang)= 0.0000 0.0000 0.0000
X= 0.0000 Y= 0.0000 Z= 0.7969 Total= 0.7969
Quadrupole Moment (Debye*Ang):
Origin of the operator (Ang)= 0.0000 0.0000 0.2961
XX= -7.1573 XY= 0.0000 XZ= 0.0000 YY= -8.2315
YZ= 0.0000 ZZ= -7.3255
In traceless form (Debye*Ang)
XX= 0.6212 XY= 0.0000 XZ= 0.0000 YY= -0.9902
YZ= 0.0000 ZZ= 0.3689
********************************************************************************
CASPT2 TIMING INFORMATION: CPU(s), I/O(s).
Inizialization 0.02 0.45
CASPT2 equations 0.01 0.15
Properties 0.06 1.45
Gradient/MS coupling 0.00 0.00
Total time 0.09 2.05
A NEW JOBIPH FILE NAMED 'JOBMIX' IS PREPARED.
********************************************************************************
The CI coefficients for the MIXED state nr. 1
--------------------------------------------------------------------------------
CI COEFFICIENTS LARGER THAN 0.50E-01
Occupation of active orbitals, and spin coupling
of open shells. (u,d: Spin up or down).
ConfOccupation Coef Weight
3 22u u0 2 -0.741301 0.549527
7 2u2 u0 2 -0.100711 0.010143
8 2u2 0u 2 0.075449 0.005693
13 2u0 2u 2 -0.630812 0.397923
14 2u0 u2 2 -0.055078 0.003034
15 u20 2u 2 0.139743 0.019528
18 20u u2 2 0.066785 0.004460
--- Stop Module: caspt2 at Fri May 19 15:22:59 BST 2006 /rc= 0 ---
--- Stop Module: auto at Fri May 19 15:23:01 BST 2006 /rc=0 ---
Output file (gzipped) ex2.out can be downloaded here. MOLDEN file (gzipped) ex2.scf.molden can be downloaded here. MOLDEN file (gzipped) ex2.rasscf.molden can be downloaded here. |
