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Software Introduction
MOLPRO | ||||||||||||||||||||
MOLPRO is an ab initio software package for molecular electronic structure calculations. The program specialises in highly accurate computations for small molecules, with extensive treatment of electron correlation. The program contains modules for running MCSCF, MRCI, DFT and Coupled-Cluster calculations, accompanied by a full set of supporting programs. The program can be run in both serial and parallel modes. The MOLPRO input files contain a series of input records. Each input record begins with a keyword, which may be followed by data or other keywords. The input is in free format, but there are some characters that can be inserted when setting up the file.
Some input records can be typed on one line and separated by a semicolon. However the following commands always occupy a whole line.
Two examples are given below. The first example is a simple HF geometry optimisation of H2O. In the second example, the energy of the H2O molecule is calculated using three different multireference methods, namely CCSD(T), CASSCF and MRCI. | ||||||||||||||||||||
Examples | ||||||||||||||||||||
Example 1. Geometry optimisation of water Example 2. CCSD(T), CASSCF and MRCI single point energy calculations of water Note: All explanations are given in red. | ||||||||||||||||||||
| Example 1. Geometry optimisation of water The following is an example of a geometry optimisation of a single water molecule at the SCF level with the 6-31G** basis set. A calculation of the frequencies is requested. The h2o.log file contains the long output of the geometry optimisation steps. The input file specifies that the low and imaginary frequencies to be printed out and a MOLDEN output file be written. | ||||||||||||||||||||
Input | ||||||||||||||||||||
h2o.com
***,h2o !A title
memory,1,m memory, 1 MW.
r=1.85,theta=104 !set geometry parameters
geometry={O; !z-matrix geometry input
H1,O,r;
H2,O,r,H1,theta}
basis=6-31g** !use Pople basis set
hf !closed-shell scf
optg !do scf geometry optimisation
frequencies; requesting frequency calculation.
print,low,img; print the low and imaginary frequencies.
put,molden,h2o.molden; write a MOLDEN file named h2o.molden .
---
Input file (gzipped) h2o.com can be downloaded here. | ||||||||||||||||||||
Output | ||||||||||||||||||||
h2o.out
Primary working directories: /scratch Location of scratch directories.
Secondary working directories: /scratch
blaslib=default
mxmblk= 32 mxmbln= 32 ncache= 8192 mindgm= 16 mindgv= 4 mindgc= 16 mindgl= 16 mindgr= 16 noblas=0 nroll=3 minvec=7
default implementation of scratch files=df
Input deck printed.
***,h2o
memory,1,m
r=1.85,theta=104 !set geometry parameters
geometry={O; !z-matrix geometry input
H1,O,r;
H2,O,r,H1,theta}
basis=6-31g** !use Pople basis set
hf !closed-shell scf
optg !do scf geometry optimization
frequencies;
print,low,img;
put,molden,h2o.molden;
---
Variables initialized (303), CPU time= 0.00 sec
Default parameters read. Elapsed time= 0.02 sec
Checking input...
Passed
1
*** PROGRAM SYSTEM MOLPRO ***
Copyright, University of Birmingham, 1997
Version 2002.6 linked 30 Jan 2004 11:08:17
**********************************************************************************************************************************
LABEL * H2O
OSF1-V5.1/columbus2(alpha) 64 bit version DATE: 3-Feb-04 TIME: 10:31:57
**********************************************************************************************************************************
Installed patches: cidps_orthp configure_xeon darwin_conf defbas_update dft_orbital_hi enest_dummy
erel_variables fujitsu-ssl2 fujitsu_conf ga_conflict2 ia64root_check lapack_init
merge_orbdom mkl60 mkl61 modelopt molden_orbital_normalization mpputil
mxm_fujitsu nec_parse opteron2 opteron6 patcher_printf posinp
pseudo_libmol2 readop_multipole_nps rpm_key sun_forte8 updui_trap_overflow wrapper_makefile
**********************************************************************************************************************************
SETTING R = 1.85000000
SETTING THETA = 104.00000000
SETTING BASIS = 6-31G**
Variable memory set to 1000000 words, buffer space 230000 words
Using spherical harmonics
Basis sets used in calculation.
Library entry O S 6-31G selected for orbital group 1
Library entry O P 6-31G selected for orbital group 1
Library entry O D 6-31G* selected for orbital group 1
Library entry H S 6-31G selected for orbital group 2
Library entry H P 6-31G** selected for orbital group 2
Integral evaluation using the program module SEWARD.
1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990
Geometry written to block 1 of record 700
Orientation using atomic masses
Molecule type: Asymmetric top, Order of principal axis = 2
Symmetry elements: X,Y
Rotational constants: 273.1674379 777.0700161 421.2525091 GHz
Point group determined automatically.
Point group C2v
ATOMIC COORDINATES
NR ATOM CHARGE X Y Z
1 O 8.00 0.000000000 0.000000000 -0.127449274
2 H1 1.00 0.000000000 1.457819894 1.011524455
3 H2 1.00 0.000000000 -1.457819894 1.011524455
Bond lengths in Bohr (Angstrom)
1--2 1.850000000 1--3 1.850000000
(0.978977911) (0.978977911)
Bond angles
2--1--3 104.00000000
NUCLEAR CHARGE: 10
NUMBER OF PRIMITIVE AOS: 42
NUMBER OF SYMMETRY AOS: 41
NUMBER OF CONTRACTIONS: 24 ( 11A1 + 4B1 + 7B2 + 2A2 )
NUMBER OF CORE ORBITALS: 1 ( 1A1 + 0B1 + 0B2 + 0A2 )
NUMBER OF VALENCE ORBITALS: 6 ( 3A1 + 1B1 + 2B2 + 0A2 )
NUCLEAR REPULSION ENERGY 8.99162654
Eigenvalues of metric
1 0.450E-01 0.222E+00 0.352E+00 0.380E+00 0.514E+00 0.933E+00 0.107E+01 0.136E+01
2 0.423E+00 0.643E+00 0.117E+01 0.177E+01
3 0.709E-01 0.166E+00 0.389E+00 0.816E+00 0.122E+01 0.131E+01 0.238E+01
4 0.571E+00 0.142E+01
Contracted 2-electron integrals neglected if value below 1.0D-11
AO integral compression algorithm 1 Integral accuracy 1.0D-11
0.262 MB (compressed) written to integral file (100.0%)
NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 13826. BUFFER LENGTH: 32768
NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 13826 RECORD LENGTH: 262144
Memory used in sort: 0.31 MW
SORT1 READ 19290. AND WROTE 12665. INTEGRALS IN 1 RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.07 SEC
SORT2 READ 12665. AND WROTE 13826. INTEGRALS IN 1 RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.23 SEC
FILE SIZES: FILE 1: 3.2 MBYTE, FILE 4: 2.1 MBYTE, TOTAL: 5.4 MBYTE
OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 3.05 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
PROGRAMS * TOTAL INT
CPU TIMES * 0.17 0.10
REAL TIME * 17.92 SEC
DISK USED * 5.80 MB
**********************************************************************************************************************************
1PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner
SCF Closed-shell calculation using the program module RHF-SCF (CLOSED SHELL)
NUMBER OF ELECTRONS: 5+ 5-
CONVERGENCE THRESHOLDS: 1.00E-06 (Density) 1.00E-07 (Energy)
MAX. NUMBER OF ITERATIONS: 60
INTERPOLATION TYPE: DIIS
INTERPOLATION STEPS: 2 (START) 1 (STEP)
LEVEL SHIFTS: 0.00 (CLOSED) 0.00 (OPEN)
Orbitals guess.
Orbital guess generated from atomic densities. Occupancy: 3 1 1 0
Molecular orbital dump at record 2100.2
ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS
1 0.000D+00 0.000D+00 -75.53552890 65.853490 0.000000 0.000000 0.134554 0
2 0.000D+00 0.156D+00 -75.84908281 81.372585 0.000000 0.000000 1.123769 1
3 0.148D+00 0.967D-01 -76.01967318 75.436661 0.000000 0.000000 0.814071 2
4 0.506D-01 0.379D-02 -76.02034646 75.460261 0.000000 0.000000 0.855162 3
5 0.537D-02 0.111D-02 -76.02041990 75.455575 0.000000 0.000000 0.864485 4
6 0.171D-02 0.300D-03 -76.02042714 75.453987 0.000000 0.000000 0.868208 5
7 0.570D-03 0.655D-04 -76.02042747 75.453824 0.000000 0.000000 0.868589 6
8 0.117D-03 0.751D-05 -76.02042747 75.454119 0.000000 0.000000 0.868615 5
9 0.926D-05 0.200D-05 -76.02042747 75.453994 0.000000 0.000000 0.868614 6
10 0.215D-05 0.856D-06 -76.02042747 75.454034 0.000000 0.000000 0.868611 7
11 0.638D-06 0.765D-07 -76.02042747 75.454034 0.000000 0.000000 0.868611 0
Final occupancy: 3 1 1 0
!RHF STATE 1.1 ENERGY -76.02042747
Nuclear energy 8.99162654
One-electron energy -122.73907103
Two-electron energy 37.72701702
Virial quotient -1.00252525
!RHF STATE 1.1 DIPOLE MOMENTS: 0.00000000 0.00000000 0.86861076
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 3.05 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
2 3 0.24 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL HF-SCF INT
CPU TIMES * 0.18 0.01 0.10
REAL TIME * 18.55 SEC
DISK USED * 5.80 MB
**********************************************************************************************************************************
Geometry optimisation calculation.
STARTING GEOMETRY OPTIMIZATION FOR HF-SCF
CONVERGENCE THRESHOLDS: 0.300D-03 (STEP) 0.300D-03 (GRADIENT) 0.100D-05 (ENERGY)
MAX. NUMBER OF STEPS: 50
*** Long output written to logfile /home/columbus_chem/ht3/temp/h2o.log ***
Making model hessian for Z-matrix coordinates
Optimization in local normal coordinates
Quadratic Steepest Descent - Minimum Search
Optimization point 1
Variable Last Current Next Gradient Hessian
E(HF-SCF) / Hartree 0.00000000 -76.02042747 0.00000000
R / BOHR 0.00000000 1.85000000 1.79413686 0.07432643 1.33064032
THETA / DEGREE 0.00000000 104.00000000 104.41232467 -0.00004022 0.00009994
Convergence: 0.00000000 (line search) 0.05632476 (total)
CPU FOR INTEGRALS: 0.1 SEC
CPU FOR HF-SCF : 0.0 SEC
CPU FOR FORCES: 0.1 SEC
Optimization point 2
Variable Last Current Next Gradient Hessian
E(HF-SCF) / Hartree -76.02042747 -76.02297423 0.00000000
R / BOHR 1.85000000 1.79413686 1.78028471 0.01388629 1.09310482
THETA / DEGREE 104.00000000 104.41232467 105.24181627 -0.00007638 0.00011736
Convergence: 0.00000000 (line search) 0.02003687 (total)
CPU FOR INTEGRALS: 0.1 SEC
CPU FOR HF-SCF : 0.0 SEC
CPU FOR FORCES: 0.1 SEC
Optimization point 3
Variable Last Current Next Gradient Hessian
E(HF-SCF) / Hartree -76.02297423 -76.02310568 0.00000000
R / BOHR 1.79413686 1.78028471 1.78077898 -0.00235163 1.40194724
THETA / DEGREE 104.41232467 105.24181627 105.67419723 -0.00004563 0.00010114
Convergence: 0.00000000 (line search) 0.00756264 (total)
CPU FOR INTEGRALS: 0.1 SEC
CPU FOR HF-SCF : 0.0 SEC
CPU FOR FORCES: 0.0 SEC
Optimization point 4
Variable Last Current Next Gradient Hessian
E(HF-SCF) / Hartree -76.02310568 -76.02312104 0.00000000
R / BOHR 1.78028471 1.78077898 1.78144900 -0.00125332 1.24642346
THETA / DEGREE 105.24181627 105.67419723 106.04915713 -0.00002134 0.00005491
Convergence: 0.00000000 (line search) 0.00657849 (total)
CPU FOR INTEGRALS: 0.0 SEC
CPU FOR HF-SCF : 0.0 SEC
CPU FOR FORCES: 0.1 SEC
Optimization point 5
Variable Last Current Next Gradient Hessian
E(HF-SCF) / Hartree -76.02312104 -76.02312549 0.00000000
R / BOHR 1.78077898 1.78144900 1.78144712 -0.00000079 1.24734965
THETA / DEGREE 105.67419723 106.04915713 106.05197721 -0.00000015 0.00005451
Convergence: 0.00000000 (line search) 0.00004926 (total)
CPU FOR INTEGRALS: 0.1 SEC
CPU FOR HF-SCF : 0.0 SEC
END OF GEOMETRY OPTIMIZATION. TOTAL CPU: 0.7 SEC
ITER. ENERGY(OLD) ENERGY(NEW) DE GRADMAX GRADNORM GRADRMS STEPMAX STEPLEN STEPRMS
1 -76.02042747 -76.02297423 -0.00254676 0.07432406 0.07436214 0.03718107 0.05585581 0.05632476 0.02816238
2 -76.02297423 -76.02310568 -0.00013146 0.01387982 0.01455959 0.00727980 0.01449777 0.02003687 0.01001843
3 -76.02310568 -76.02312104 -0.00001536 0.00261073 0.00351630 0.00175815 0.00754573 0.00756264 0.00378132
4 -76.02312104 -76.02312549 -0.00000444 0.00125505 0.00175074 0.00087537 0.00654333 0.00657849 0.00328925
5 -76.02312549 -76.02312549 0.00000000 0.00000869 0.00000872 0.00000436 0.00004922 0.00004926 0.00002463
Geometry written to block 1 of record 700
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 3.05 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
2 3 0.24 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL OPTG HF-SCF INT
CPU TIMES * 0.87 0.69 0.01 0.10
REAL TIME * 34.15 SEC
DISK USED * 5.82 MB
**********************************************************************************************************************************
********************************************************************************************************************************
PROGRAM * FREQUENCIES Author: F. Eckert
CALCULATING HARMONIC VIBRATIONAL FREQUENCIES FOR HF-SCF
Numerically approximating hessian using central gradient differences
Total number of displacements: 10
Incrementing variable OX by +/- 0.010 BOHR
Incrementing variable OY by +/- 0.010 BOHR
Incrementing variable OZ by +/- 0.010 BOHR
Incrementing variable H1X by +/- 0.010 BOHR
Incrementing variable H1Y by +/- 0.010 BOHR
Incrementing variable H1Z by +/- 0.010 BOHR
FREQUENCIES * CALCULATION OF HARMONIC VIBRATIONAL SPECTRA FOR HF-SCF
Permanent Dipole Moment [debye]
1- 3 0.000000 0.000000 2.142572
Dipole Moment Norm 2.1425724 [debye]
Dipole Moment Derivatives [debye/ang]
1 2 3 4 5 6 7 8
1 -3.7787913 0.0000000 0.0000000 1.8895678 0.0000000 0.0000000 1.8895678 0.0000000
2 0.0000000 -2.5535405 0.0000000 0.0000000 1.2768945 -0.4612616 0.0000000 1.2768945
3 0.0000000 0.0000000 -2.2119599 0.0000000 -0.2968339 1.1060220 0.0000000 0.2968339
9
1 0.0000000
2 0.4612616
3 1.1060220
Imaginary Vibration Wavenumber
Nr [1/cm]
1 27.24
2 5.82
3 2.99
Low Vibration Wavenumber
Nr [1/cm]
1 6.20
2 14.47
3 22.31
Vibration Wavenumber
Nr [1/cm]
1 1769.71
2 4152.96
3 4270.19
FREQUENCIES * CALCULATION OF NORMAL MODES FOR HF-SCF
Atomic Coordinates
Nr Atom Charge X Y Z
1 O 8.00 0.000000000 0.000000000 -0.119894175
2 H1 1.00 0.000000000 1.423213076 0.951562027
3 H2 1.00 0.000000000 -1.423213076 0.951562027
Frequencies dumped to record 5400.2
Gradient norm at reference geometry: 0.10077D-06
Normal Modes
1 2 3
Wavenumbers [cm-1] 1769.71 4152.96 4270.19
Intensities [km/mol] 106.77 16.13 58.91
Intensities [relative] 96.63 14.60 53.32
OX 0.00000 0.00000 0.00000
OY 0.00000 -0.00002 -0.06821
OZ -0.06813 0.04849 -0.00001
H1X 0.00000 0.00000 0.00000
H1Y -0.40831 -0.57370 0.54150
H1Z 0.54076 -0.38470 0.40765
H2X 0.00000 0.00000 0.00000
H2Y 0.40838 0.57402 0.54118
H2Z 0.54087 -0.38493 -0.40742
Normal Modes of imaginary frequencies
1 2 3
Wavenumbers [cm-1] 27.24 5.82 2.99
Intensities [km/mol] 110.49 2.04 0.31
Intensities [relative] 100.00 1.85 0.28
OX 0.00000 0.00000 0.23770
OY 0.03695 -0.16009 0.00000
OZ 0.03249 0.17583 0.00000
H1X 0.00000 0.00000 0.17659
H1Y -0.39093 -0.10187 0.00000
H1Z 0.60086 0.09849 0.00000
H2X 0.00000 0.00000 0.25319
H2Y -0.39086 -0.10191 0.00000
H2Z -0.53578 0.25313 0.00000
Normal Modes of low/zero frequencies
1 2 3
Wavenumbers [cm-1] 6.20 14.47 22.31
Intensities [km/mol] 0.00 0.00 0.00
Intensities [relative] 0.00 0.00 0.00
OX 0.00000 0.01193 -0.07656
OY 0.17566 0.00000 0.00000
OZ 0.15342 0.00000 0.00000
H1X 0.00000 0.72379 0.66111
H1Y 0.19959 0.00000 0.00000
H1Z 0.12162 0.00000 0.00000
H2X 0.00000 -0.68264 0.67972
H2Y 0.19955 0.00000 0.00000
H2Z 0.18517 0.00000 0.00000
Zero point energy: 0.02322103 [H] 5096.43 [1/CM] 60.97 [KJ/MOL]
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 3.05 600 700 500 960 900 950 970 1000 1100 1400
BASINP GEOM VAR ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
2 5 0.25 700 1000 2100 5300 5400
GEOM BASIS RHF HESS FREQ
PROGRAMS * TOTAL FREQ OPTG HF-SCF INT
CPU TIMES * 2.92 2.03 0.69 0.01 0.10
REAL TIME * 49.83 SEC
DISK USED * 6.70 MB
**********************************************************************************************************************************
h2o.molden produced as requested.
Dump information in style MOLDEN to h2o.molden
Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Occupation numbers read from record 2100.2 Type=RHF/RHF (state 1.1)
Orbital energies read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Redundancy group numbers read from rec 2100.2 Type=RHF/RHF (state 1.1)
DUMP ORBITAL 1.1 AS ORBITAL 1 occ= 2.0000 eig= -20.5543 GROUP= 2
DUMP ORBITAL 2.1 AS ORBITAL 2 occ= 2.0000 eig= -1.3461 GROUP= 2
DUMP ORBITAL 1.3 AS ORBITAL 3 occ= 2.0000 eig= -0.7137 GROUP= 2
DUMP ORBITAL 3.1 AS ORBITAL 4 occ= 2.0000 eig= -0.5679 GROUP= 2
DUMP ORBITAL 1.2 AS ORBITAL 5 occ= 2.0000 eig= -0.4971 GROUP= 2
Frequency information read from record 5400.2
**********************************************************************************************************************************
Summary of energies for initial geometry and final optimised geometry.
OPTG HF-SCF
-76.02312549 -76.02042747
**********************************************************************************************************************************
Variable memory released
Output file (gzipped) h2o.out can be downloaded here. Output file (gzipped) h2o.log can be downloaded here. Output file (gzipped) h2o.molden can be downloaded here. | ||||||||||||||||||||
| Example 2. CCSD(T), CASSCF and MRCI single point energy calculations of water
In this example, we illustrate some of the post-SCF methods available in MOLPRO. In this case, CCSD(T), CASSCF and MRCI calculations are carried out after the initial HF calculation. The input is set out in the following way. First, the geometry of water is specified along with the chosen basis set. Then the corresponding calculations are requested through the keywords, hf, ccsd(t), casscf and mrci. Normally, it is necessary to define the orbital subspaces for the CASSCF and MRCI calculations using the core, closed and occ keywords. If nothing is specified, the default for both methods is to take the information from the most recent MCSCF calculation, or, if there is none, to use a full valence space. For example, in this case, the oxygen 1s orbital will be taken to be closed-shell, while the OH σ and σ* orbitals and the two oxygen n orbitals will make up the CASSCF active space (i.e. CAS(8,6). It is advisable to use the print, orbitals option to check that the correct active space is being used. The MRCI calculation will use the same active space as it will take its information from the CASSCF calculation. The number of electrons, spatial symmetry (irrep), spin and charge of the state can be specified using the wf keyword. The default is to take the number of electrons to be the sum of the nuclear charges, irrep to be 1, the spin to be 0 or 1, and the charge to be 0, so in many cases this is not needed. Below is an example on how to specify the CASSCF orbitals for a water molecule. casscf occ,4,1,2,0; 7 orbitals (4 A1, 1 B1, 2 B2, 0 A2). closed,1,0,0,0; Oxygen 1s orbital kept doubly occupied. wf,10,1,0,0; print,orbitals; | ||||||||||||||||||||
Input | ||||||||||||||||||||
h2o_vtz.com
***,h2o !A title
r=1.85,theta=104 !set geometry parameters
geometry={o; !z-matrix geometry input
h1,O,r;
h2,O,r,H1,theta}
basis=vtz !use VTZ basis
hf !closed-shell scf
ccsd(t) !do ccsd(t) calculation
casscf !do casscf calculation
mrci !do mrci calculation
---
Input file (gzipped) h2o_vtz.com can be downloaded here. | ||||||||||||||||||||
Output | ||||||||||||||||||||
h2o_vtz.out
Primary working directories: /scratch
Secondary working directories: /scratch
blaslib=default
mxmblk= 32 mxmbln= 32 ncache= 8192 mindgm= 16 mindgv= 4 mindgc= 16 mindgl= 16 mindgr= 16 noblas=0 nroll=3 minvec=7
default implementation of scratch files=df
***,h2o
r=1.85,theta=104 !set geometry parameters
geometry={o; !z-matrix geometry input
h1,O,r;
h2,O,r,H1,theta}
basis=vtz !use VTZ basis
hf !closed-shell scf
ccsd(t) !do ccsd(t) calculation
casscf !do casscf calculation
mrci !do mrci calculation
---
Variables initialized (303), CPU time= 0.02 sec
Default parameters read. Elapsed time= 0.33 sec
Checking input...
Passed
1
*** PROGRAM SYSTEM MOLPRO ***
Copyright, University of Birmingham, 1997
Version 2002.6 linked 30 Jan 2004 11:08:17
**********************************************************************************************************************************
LABEL * H2O
OSF1-V5.1/columbus1(alpha) 64 bit version DATE: 3-Feb-04 TIME: 10:31:17
**********************************************************************************************************************************
Installed patches: cidps_orthp configure_xeon darwin_conf defbas_update dft_orbital_hi enest_dummy
erel_variables fujitsu-ssl2 fujitsu_conf ga_conflict2 ia64root_check lapack_init
merge_orbdom mkl60 mkl61 modelopt molden_orbital_normalization mpputil
mxm_fujitsu nec_parse opteron2 opteron6 patcher_printf posinp
pseudo_libmol2 readop_multipole_nps rpm_key sun_forte8 updui_trap_overflow wrapper_makefile
**********************************************************************************************************************************
SETTING R = 1.85000000
SETTING THETA = 104.00000000
SETTING BASIS = VTZ
Variable memory set to 8000000 words, buffer space 230000 words
Using spherical harmonics
cc-pVTZ basis sets used.
Library entry O S cc-pVTZ selected for orbital group 1
Library entry O P cc-pVTZ selected for orbital group 1
Library entry O D cc-pVTZ selected for orbital group 1
Library entry O F cc-pVTZ selected for orbital group 1
Library entry H S cc-pVTZ selected for orbital group 2
Library entry H P cc-pVTZ selected for orbital group 2
Library entry H D cc-pVTZ selected for orbital group 2
1PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990
Geometry written to block 1 of record 700
Orientation using atomic masses
Molecule type: Asymmetric top, Order of principal axis = 2
Symmetry elements: X,Y
Rotational constants: 273.1674379 777.0700161 421.2525091 GHz
Point group C2v
ATOMIC COORDINATES
NR ATOM CHARGE X Y Z
1 O 8.00 0.000000000 0.000000000 -0.127449274
2 H1 1.00 0.000000000 1.457819894 1.011524455
3 H2 1.00 0.000000000 -1.457819894 1.011524455
Bond lengths in Bohr (Angstrom)
1--2 1.850000000 1--3 1.850000000
(0.978977911) (0.978977911)
Bond angles
2--1--3 104.00000000
NUCLEAR CHARGE: 10
NUMBER OF PRIMITIVE AOS: 81
NUMBER OF SYMMETRY AOS: 74
NUMBER OF CONTRACTIONS: 58 ( 23A1 + 11B1 + 17B2 + 7A2 ) Orbital symmetries.
NUMBER OF CORE ORBITALS: 1 ( 1A1 + 0B1 + 0B2 + 0A2 ) Oxygen 1s orbital taken to be a core orbital.
NUMBER OF VALENCE ORBITALS: 6 ( 3A1 + 1B1 + 2B2 + 0A2 )
NUCLEAR REPULSION ENERGY 8.99162654
Eigenvalues of metric
1 0.271E-02 0.622E-02 0.115E-01 0.435E-01 0.869E-01 0.117E+00 0.177E+00 0.274E+00
2 0.415E-01 0.113E+00 0.259E+00 0.453E+00 0.533E+00 0.718E+00 0.110E+01 0.133E+01
3 0.491E-02 0.849E-02 0.484E-01 0.721E-01 0.963E-01 0.181E+00 0.282E+00 0.339E+00
4 0.124E+00 0.325E+00 0.552E+00 0.893E+00 0.121E+01 0.132E+01 0.228E+01
Contracted 2-electron integrals neglected if value below 1.0D-11
AO integral compression algorithm 1 Integral accuracy 1.0D-11
2.884 MB (compressed) written to integral file ( 63.0%)
NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 396151. BUFFER LENGTH: 32768
NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 396151 RECORD LENGTH: 524288
Memory used in sort: 0.95 MW
SORT1 READ 562034. AND WROTE 366996. INTEGRALS IN 2 RECORDS. CPU TIME: 0.08 SEC, REAL TIME: 0.28 SEC
SORT2 READ 366996. AND WROTE 396151. INTEGRALS IN 11 RECORDS. CPU TIME: 0.05 SEC, REAL TIME: 0.35 SEC
FILE SIZES: FILE 1: 5.9 MBYTE, FILE 4: 8.4 MBYTE, TOTAL: 14.3 MBYTE
OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 4.95 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
PROGRAMS * TOTAL INT
CPU TIMES * 0.65 0.58
REAL TIME * 5.90 SEC
DISK USED * 14.79 MB
**********************************************************************************************************************************
1PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner
HF-SCF calculation.
NUMBER OF ELECTRONS: 5+ 5-
CONVERGENCE THRESHOLDS: 1.00E-05 (Density) 1.00E-07 (Energy)
MAX. NUMBER OF ITERATIONS: 60
INTERPOLATION TYPE: DIIS
INTERPOLATION STEPS: 2 (START) 1 (STEP)
LEVEL SHIFTS: 0.00 (CLOSED) 0.00 (OPEN)
Orbital guess generated from atomic densities. Occupancy: 3 1 1 0
Molecular orbital dump at record 2100.2
ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS
1 0.000D+00 0.000D+00 -76.01605353 77.481973 0.000000 0.000000 1.175605 0
2 0.000D+00 0.190D-01 -76.04405724 73.988619 0.000000 0.000000 0.712336 1
3 0.327D-01 0.116D-01 -76.05457472 75.488741 0.000000 0.000000 0.817563 2
4 0.110D-01 0.110D-02 -76.05477703 75.407932 0.000000 0.000000 0.810968 3
5 0.162D-02 0.322D-03 -76.05479994 75.420140 0.000000 0.000000 0.807748 4
6 0.589D-03 0.620D-04 -76.05480118 75.418544 0.000000 0.000000 0.806930 5
7 0.137D-03 0.107D-04 -76.05480122 75.418670 0.000000 0.000000 0.806757 6
8 0.277D-04 0.154D-05 -76.05480122 75.418609 0.000000 0.000000 0.806732 5
9 0.345D-05 0.378D-06 -76.05480122 75.418646 0.000000 0.000000 0.806734 0
Final occupancy: 3 1 1 0
!RHF STATE 1.1 ENERGY -76.05480122
Nuclear energy 8.99162654
One-electron energy -122.75575089
Two-electron energy 37.70932313
Virial quotient -1.00172525
!RHF STATE 1.1 DIPOLE MOMENTS: 0.00000000 0.00000000 0.80673372
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 4.95 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER
2 3 0.26 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL HF-SCF INT
CPU TIMES * 0.83 0.17 0.58
REAL TIME * 6.33 SEC
DISK USED * 14.79 MB
**********************************************************************************************************************************
CCSD(T) calculation.
1PROGRAM * CCSD (Closed-shell coupled cluster) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992
Convergence thresholds: THRVAR = 1.00D-10 THRDEN = 1.00D-06
CCSD(T) terms to be evaluated (factor= 1.000)
Number of core orbitals: 1 ( 1 0 0 0 )
Number of closed-shell orbitals: 4 ( 2 1 1 0 )
Number of external orbitals: 53 ( 20 10 16 7 )
Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Number of N-1 electron functions: 4
Number of N-2 electron functions: 10
Number of singly external CSFs: 66
Number of doubly external CSFs: 5929
Total number of CSFs: 5996
Length of J-op integral file: 0.00 MB
Length of K-op integral file: 0.09 MB
Length of 3-ext integral record: 0.00 MB
Integral transformation finished. Total CPU: 0.05 sec, npass= 1 Memory used: 0.12 MW
Reference energy: -76.05480122
MP2 correlation energy: -0.26309697
MP2 total energy: -76.31789819
ITER. NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) DIIS TIME
1 1.06180195 -0.26314267 -76.31794389 -0.00004570 -0.00526701 0.48D-03 0.87D-03 0 0 0.12
2 1.06492042 -0.26749818 -76.32229940 -0.00435551 -0.00035374 0.11D-04 0.10D-03 0 0 0.17
3 1.06584084 -0.26826100 -76.32306222 -0.00076282 -0.00005758 0.40D-05 0.16D-04 1 1 0.22
4 1.06656948 -0.26885710 -76.32365831 -0.00059610 -0.00000161 0.16D-06 0.44D-06 2 2 0.27
5 1.06661082 -0.26885430 -76.32365552 0.00000280 -0.00000018 0.71D-07 0.34D-07 3 3 0.32
6 1.06662586 -0.26885883 -76.32366005 -0.00000453 -0.00000002 0.10D-07 0.25D-08 4 4 0.37
7 1.06662977 -0.26886065 -76.32366186 -0.00000181 0.00000000 0.10D-08 0.22D-09 5 5 0.43
8 1.06663038 -0.26886016 -76.32366138 0.00000049 0.00000000 0.64D-10 0.33D-10 6 6 0.48
Norm of t1 vector: 0.00074347 S-energy: 0.00000001 T1 diagnostic: 0.00681668
Norm of t2 vector: 0.06588691 P-energy: -0.26886017
Memory could be reduced to 0.6 Mword without degradation in triples
CPU time for triples: 0.22 sec
RESULTS
=======
!CCSD ENERGY -76.323661377664
!CCSD[T] ENERGY -76.331695799361 (Triples contribution -0.00803442)
!CCSD-T ENERGY -76.331348354980 (Triples contribution -0.00768698)
Reference energy -76.054801218408
Correlation energy -0.276690988983
!CCSD(T) ENERGY -76.331492207391 (Triples contribution -0.00783083)
Program statistics:
Available memory in ccsd: 7999868
Min. memory needed in ccsd: 31747
Max. memory used in ccsd: 36013
Max. memory used in cckext: 65616 ( 8 integral passes)
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 5.72 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700 1380
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER JKOP
2 3 0.26 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL CCSD(T) HF-SCF INT
CPU TIMES * 1.55 0.72 0.17 0.58
REAL TIME * 8.28 SEC
DISK USED * 14.79 MB
**********************************************************************************************************************************
CASSCF calculation.
1PROGRAM * MULTI (Direct Multiconfiguration SCF) Authors: P.J. Knowles, H.-J. Werner (1984) S.T. Elbert (1988)
Default active space (full valence).
Number of closed-shell orbitals: 1 ( 1 0 0 0 ) Oxygen 1s orbital.
Number of active orbitals: 6 ( 3 1 2 0 ) OH σ and σ* orbitals, 2 O lone pairs.
Number of external orbitals: 51 ( 19 10 15 7 )
State symmetry 1
Number of electrons: 8 Spin symmetry=Singlet Space symmetry=1
Number of states: 1
Number of CSFs: 37 ( 65 determinants, 225 intermediate states)
Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Wavefunction dump at record 2140.2
Convergence thresholds 0.10E-01 (gradient) 0.10E-05 (energy) 0.10E-02 (step length)
Number of orbital rotations 119 ( 3 Core/Active 19 Core/Virtual 0 Active/Active 97 Active/Virtual)
Total number of variables = 184
ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME
1 37 11 0 -76.05822244 -76.11097810 -0.05275566 0.01396069 0.00255768 0.00209399 0.11D+01 0.10
2 33 9 0 -76.10940589 -76.11006211 -0.00065622 0.02860207 0.00000471 0.00001000 0.10D+00 0.20
3 31 7 0 -76.11006258 -76.11006259 0.00000000 0.00006461 0.00000003 0.00000008 0.21D-03 0.28
** WVFN **** CONVERGENCE REACHED, FINAL GRADIENT: 0.23D-07
First order spin density matrix for state 1.1 saved on record 2140.2 (density set 1)
First order charge density matrix for state 1.1 saved on record 2140.2 (density set 2)
Results for state 1.1
---------------------
!MC STATE 1.1 ENERGY -76.11006259
Nuclear energy 8.99162654
Kinetic energy 76.07018574
One electron energy -122.70948079
Two electron energy 37.60779166
Virial ratio 2.00052421
!MC STATE 1.1 DIPOLE MOMENTS: 0.00000000 0.00000000 0.74318632 a.u. 0.000000 0.000000 1.888867 Debye
Natural orbital dump at molpro section 2140.2 (Orbital set 2)
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 5.72 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700 1380
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER JKOP
2 4 0.33 700 1000 2100 2140
GEOM BASIS RHF MCSCF
PROGRAMS * TOTAL CASSCF CCSD(T) HF-SCF INT
CPU TIMES * 1.88 0.33 0.72 0.17 0.58
REAL TIME * 9.15 SEC
DISK USED * 14.79 MB
**********************************************************************************************************************************
MRCI calculation.
1PROGRAM * CI (Multireference internally contracted CI) Authors: H.-J. Werner, P.J. Knowles, 1987
Convergence thresholds: THRVAR = 1.00D-10 THRDEN = 1.00D-06
Number of optimized states: 1 Roots: 1
Number of reference states: 1 Roots: 1
Reference symmetry: 1 Singlet
Maximum shell inside CICON 6
Maximum number of shells reduced from 6 to 5
Maximum number of spin couplings: 14
Reference space: 34 conf 37 CSFs
N elec internal: 90 conf 105 CSFs
N-1 el internal: 126 conf 210 CSFs
N-2 el internal: 141 conf 364 CSFs
Number of electrons in valence space: 8
Maximum number of open shell orbitals in reference space: 4
Maximum number of open shell orbitals in internal spaces: 8
Number of core orbitals: 1 ( 1 0 0 0 )
Number of active orbitals: 6 ( 3 1 2 0 )
Number of external orbitals: 51 ( 19 10 15 7 )
Molecular orbitals read from record 2140.2 Type=MCSCF/NATURAL (state 1.1) Orbitals taken from previous calculation.
Coulomb and exchange operators available. No transformation done.
Number of p-space configurations: 1
Reference wavefunction optimized for reference space (refopt=1)
State Reference Energy
1 -76.11006259 CASSCF energy.
Number of blocks in overlap matrix: 8 Smallest eigenvalue: 0.14D-02
Number of N-2 electron functions: 36
Number of N-1 electron functions: 210
Number of internal configurations: 37
Number of singly external configurations: 2773
Number of doubly external configurations: 12460
Total number of contracted configurations: 15270
Total number of uncontracted configurations: 122164
Diagonal Coupling coefficients finished. Storage: 15031 words, CPU-Time: 0.02 seconds.
Energy denominators for pairs finished in 1 passes. Storage: 14894 words, CPU-time: 0.00 seconds.
ITER. STATE ROOT NORM CORR.ENERGY TOTAL ENERGY ENERGY CHANGE DEN1 VAR(S) VAR(P) TIME
1 1 1 1.00000000 0.00000000 -76.11006259 0.00000000 -0.21818870 0.23D-01 0.27D-01 0.08
2 1 1 1.04274068 -0.20176712 -76.31182971 -0.20176712 -0.00767367 0.10D-02 0.91D-03 0.27
3 1 1 1.04408188 -0.20903693 -76.31909952 -0.00726981 -0.00041999 0.48D-04 0.51D-04 0.48
4 1 1 1.04542122 -0.20951210 -76.31957468 -0.00047517 -0.00002969 0.40D-05 0.33D-05 0.68
5 1 1 1.04563643 -0.20954426 -76.31960684 -0.00003216 -0.00000222 0.38D-06 0.23D-06 0.88
6 1 1 1.04564203 -0.20954661 -76.31960920 -0.00000236 -0.00000019 0.34D-07 0.18D-07 1.10
7 1 1 1.04563874 -0.20954682 -76.31960941 -0.00000021 -0.00000002 0.29D-08 0.18D-08 1.28
8 1 1 1.04563922 -0.20954684 -76.31960943 -0.00000002 0.00000000 0.32D-09 0.18D-09 1.47
9 1 1 1.04563956 -0.20954684 -76.31960943 0.00000000 0.00000000 0.37D-10 0.20D-10 1.65
=====================================
Analysis of CPU times by interactions
-------------------------------------
I S P
I 1.0%
S 1.0% 7.1%
P 2.0% 12.1% 33.3%
Initialization: 5.1%
Other: 38.4%
Total CPU: 1.7 seconds
=====================================
Reference coefficients greater than 0.0500000
---------------------------------------------
220220 0.9684457
2+-2+- -0.0709017
220202 -0.0670173
202220 -0.0656726
Coefficients of singly external configurations greater than 0.0500000
---------------------------------------------------------------------
2-+-20 2.2 -0.0540534
RESULTS FOR STATE 1.1
=====================
Coefficient of reference function: C(0) = 0.97772512
Energy contributions of configuration classes
Class Norm ECORR1 ECORR2
---------------------------------------------------
Internals 0.00042479 0.00000000 -0.00008509
Singles 0.01796464 -0.06312743 -0.06394470
Pairs 0.02769430 -0.14641942 -0.14551706
Total 1.04608373 -0.20954685 -0.20954684
---------------------------------------------------
Reference energy -76.11006259
Nuclear energy 8.99162654
Kinetic energy 76.27755651
One electron energy -122.54812773
Two electron energy 37.23689175
Virial quotient -1.00055131
Correlation energy -0.20954684
!MRCI STATE 1.1 ENERGY -76.31960943
Cluster corrected energies -76.32917305 (Davidson) -76.32917305 (externals)
-76.32694665 (Pople) -76.32694665 (externals)
!MRCI STATE 1.1 DIPOLE MOMENTS: 0.00000000 0.00000000 0.75086316 a.u. 0.000000 0.000000 1.908379 Debye
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 5.72 600 500 700 960 900 950 970 1000 1100 1400
BASINP VAR GEOM ABASIS SYMINP ZMAT AOBASIS BASIS S T
1410 1200 1210 1080 1600 129 1650 1300 1700 1380
V H0 H01 AOSYM SMH P2S MOLCAS ERIS OPER JKOP
2 4 0.33 700 1000 2100 2140
GEOM BASIS RHF MCSCF
PROGRAMS * TOTAL MRCI CASSCF CCSD(T) HF-SCF INT
CPU TIMES * 3.57 1.69 0.33 0.72 0.17 0.58
REAL TIME * 11.95 SEC
DISK USED * 14.79 MB
**********************************************************************************************************************************
Summary of energies from each energy calculation.
MRCI CASSCF CCSD(T) HF-SCF
-76.31960943 -76.11006259 -76.33149221 -76.05480122
**********************************************************************************************************************************
Variable memory released
Output file (gzipped) h2o_vtz.out can be downloaded here. |