[molpro-user] MP2 pair energies
Matthias Heger
heger at ualberta.ca
Tue Dec 5 22:02:57 CET 2017
I am a bit confused about the MP2 pair energies reported in my calculations. Specifically, my attached example yields:
> SCS-MP2 correlation energy: -0.198842375046 (PS= 1.200000 PT= 0.333333)
> (...)
> MP2 singlet pair energy -0.126127623239
> MP2 triplet pair energy -0.076321972220
Scaling the pair energies manually and adding them yields a different energy (-0.176792... Hartree) than given above.
In addition, I tricked the SCS calculation to only pick up the singlet or triplet pairs with SCSFACS and SCSFACT. That yields SCS correlation energies different from the corresponding pair energies in the output.
Am I interpreting this wrong?
Best,
Matthias
--
Dr. Matthias Heger
Department of Chemistry, University of Alberta
11227 Saskatchewan Drive NW
Edmonton, AB T6G 2G2, Canada
Office: CCIS 4-151
Lab: CCIS 4-108
Email: heger at ualberta.ca
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Primary working directories : /scratch/mheger/Molpro
Secondary working directories : /scratch/mheger/Molpro
Wavefunction directory : /home/mheger/wfu/
Main file repository : /scratch/mheger/Molpro/
SHA1 : 2a61902bb8da2b22da9e50fa118b040149413476
NAME : 2015.1.27
ARCHNAME : linux/x86_64
FC : /opt/intel/composer_xe_2015.1.133/bin/intel64/ifort
BLASLIB : -Wl,-_start-group /opt/intel/mkl/lib/intel64/libmkl_intel_ilp64.a /opt/intel/mkl/lib/intel64/libmkl_intel_thread.a /opt/intel/mkl/lib/intel64/libmkl_core.a -Wl,-_end-group
id : ualberta
Nodes nprocs
gra-login1 1
Using customized tuning parameters: mindgm=1; mindgv=20; mindgc=4; mindgr=1; noblas=0; minvec=7
default implementation of scratch files=df
***,scaling
memory,10,m
basis,vdz
symmetry,nosym
geomtyp=xyz
geometry={
3
DF-MP2/VDZ ENERGY=-76.22861577
H 0.0000000000 -0.7493088668 0.1307084628
O 0.0000000000 -0.0000000002 0.7385830744
H 0.0000000000 0.7493088670 0.1307084628
}
hf
mp2
mp2,scsfacs=1,scsfact=0
mp2,scsfacs=0,scsfact=1
Variables initialized (889), CPU time= 0.01 sec
Commands initialized (702), CPU time= 0.01 sec, 572 directives.
Default parameters read. Elapsed time= 0.10 sec
Checking input...
Passed
1
*** PROGRAM SYSTEM MOLPRO ***
Copyright, TTI GmbH Stuttgart, 2015
Version 2015.1 linked Nov 22 2017 10:14:24
**********************************************************************************************************************************
LABEL * scaling
64 bit serial version DATE: 05-Dec-17 TIME: 15:58:44
**********************************************************************************************************************************
SHA1: 2a61902bb8da2b22da9e50fa118b040149413476
**********************************************************************************************************************************
Variable memory set to 10000000 words, buffer space 230000 words
SETTING BASIS = VDZ
SETTING GEOMTYP = XYZ
ZSYMEL=NOSYM
Recomputing integrals since basis changed
Using spherical harmonics
Library entry H S cc-pVDZ selected for orbital group 1
Library entry H P cc-pVDZ selected for orbital group 1
Library entry O S cc-pVDZ selected for orbital group 2
Library entry O P cc-pVDZ selected for orbital group 2
Library entry O D cc-pVDZ selected for orbital group 2
PROGRAM * SEWARD (Integral evaluation for generally contracted gaussian basis sets) Author: Roland Lindh, 1990
Geometry written to block 1 of record 700
Point group C1
ATOMIC COORDINATES
NR ATOM CHARGE X Y Z
1 H 1.00 0.000000000 -1.415988541 0.247003197
2 O 8.00 0.000000000 -0.000000000 1.395719731
3 H 1.00 0.000000000 1.415988541 0.247003197
Bond lengths in Bohr (Angstrom)
1-2 1.823341225 2-3 1.823341226
( 0.964870624) ( 0.964870624)
Bond angles
1-2-3 101.89881925
NUCLEAR CHARGE: 10
NUMBER OF PRIMITIVE AOS: 41
NUMBER OF SYMMETRY AOS: 40
NUMBER OF CONTRACTIONS: 24 ( 24A )
NUMBER OF CORE ORBITALS: 1 ( 1A )
NUMBER OF VALENCE ORBITALS: 6 ( 6A )
NUCLEAR REPULSION ENERGY 9.12820933
EXTRA SYMMETRY OF AOS IN SYMMETRY 1: 1 1 2 1 1 1 1 1 2 1 1 2 1 1 1 2 2 1 1 1 1 2 1 1
Eigenvalues of metric
1 0.175E-01 0.460E-01 0.516E-01 0.987E-01 0.160E+00 0.172E+00 0.183E+00 0.223E+00
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 ( 77.4%)
NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 45150. BUFFER LENGTH: 32768
NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 45150 RECORD LENGTH: 524288
Memory used in sort: 0.60 MW
SORT1 READ 62044. AND WROTE 21666. INTEGRALS IN 1 RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.00 SEC
SORT2 READ 21666. AND WROTE 45150. INTEGRALS IN 1 RECORDS. CPU TIME: 0.01 SEC, REAL TIME: 0.00 SEC
FILE SIZES: FILE 1: 20.2 MBYTE, FILE 4: 4.2 MBYTE, TOTAL: 24.4 MBYTE
OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 20.06 500 610 700 900 950 970 1000 129 960 1100
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200 1210 1080 1600 1650 1300 1700
T V H0 H01 AOSYM SMH MOLCAS ERIS OPER
PROGRAMS * TOTAL INT
CPU TIMES * 0.14 0.03
REAL TIME * 4.61 SEC
DISK USED * 24.70 MB
**********************************************************************************************************************************
PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner
NUMBER OF ELECTRONS: 5+ 5- SPACE SYMMETRY=1 SPIN SYMMETRY: Singlet
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. Full valence occupancy: 7
Molecular orbital dump at record 2100.2
Initial occupancy: 5
ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS ORB.
1 0.000D+00 0.000D+00 -75.98733388 77.762660 -0.00000 0.00000 -1.17932 0 start
2 0.000D+00 0.220D-01 -76.01731528 74.490673 -0.00000 0.00000 -0.76544 1 diag
3 0.463D-01 0.117D-01 -76.02597546 75.824791 -0.00000 0.00000 -0.84475 2 diag
4 0.153D-01 0.131D-02 -76.02619750 75.726642 -0.00000 0.00000 -0.83188 3 diag
5 0.280D-02 0.359D-03 -76.02621630 75.739137 -0.00000 0.00000 -0.82808 4 diag
6 0.904D-03 0.564D-04 -76.02621690 75.739071 -0.00000 0.00000 -0.82745 5 diag
7 0.144D-03 0.812D-05 -76.02621692 75.739009 -0.00000 0.00000 -0.82735 6 diag
8 0.253D-04 0.667D-06 -76.02621692 75.739001 -0.00000 0.00000 -0.82735 7 diag
9 0.173D-05 0.872D-07 -76.02621692 75.738997 -0.00000 0.00000 -0.82735 0 orth
Final occupancy: 5
!RHF STATE 1.1 Energy -76.026216915094
Nuclear energy 9.12820933
One-electron energy -123.02392454
Two-electron energy 37.86949829
Virial quotient -1.00082407
!RHF STATE 1.1 Dipole moment -0.00000000 0.00000000 -0.82734645
Dipole moment /Debye -0.00000000 0.00000000 -2.10276719
Orbital energies:
1.1 2.1 3.1 4.1 5.1 6.1 7.1
-20.553196 -1.334936 -0.690246 -0.570526 -0.493561 0.183733 0.255404
HOMO 5.1 -0.493561 = -13.4305eV
LUMO 6.1 0.183733 = 4.9996eV
LUMO-HOMO 0.677294 = 18.4301eV
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 20.06 500 610 700 900 950 970 1000 129 960 1100
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200 1210 1080 1600 1650 1300 1700
T V H0 H01 AOSYM SMH MOLCAS ERIS OPER
2 4 2.79 700 1000 520 2100
GEOM BASIS MCVARS RHF
PROGRAMS * TOTAL HF INT
CPU TIMES * 0.16 0.02 0.03
REAL TIME * 4.66 SEC
DISK USED * 24.70 MB
**********************************************************************************************************************************
PROGRAM * MP2 (Closed-shell) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992
Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06
Number of core orbitals: 1 ( 1 )
Number of closed-shell orbitals: 4 ( 4 )
Number of external orbitals: 19 ( 19 )
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: 76
Number of doubly external CSFs: 2926
Total number of CSFs: 3003
Length of J-op integral file: 0.00 MB
Length of K-op integral file: 0.07 MB
Integral transformation finished. Total CPU: 0.00 sec, npass= 1 Memory used: 0.08 MW
Memory needed for MP2: 0.00 MW
SCS-MP2 correlation energy: -0.198842375046 (PS= 1.200000 PT= 0.333333)
SCS-MP2 total energy: -76.225059290140
Reference energy -76.026216915094
MP2 singlet pair energy -0.126127623239
MP2 triplet pair energy -0.076321972220
MP2 correlation energy -0.202449595459
!MP2 total energy -76.228666510553
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 20.14 500 610 700 900 950 970 1000 129 960 1100
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200 1210 1080 1600 1650 1300 1700 1380
T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP
2 4 2.79 700 1000 520 2100
GEOM BASIS MCVARS RHF
PROGRAMS * TOTAL MP2 HF INT
CPU TIMES * 0.18 0.02 0.02 0.03
REAL TIME * 7.49 SEC
DISK USED * 24.70 MB
**********************************************************************************************************************************
PROGRAM * MP2 (Closed-shell) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992
Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06
Number of core orbitals: 1 ( 1 )
Number of closed-shell orbitals: 4 ( 4 )
Number of external orbitals: 19 ( 19 )
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: 76
Number of doubly external CSFs: 2926
Total number of CSFs: 3003
Length of J-op integral file: 0.00 MB
Length of K-op integral file: 0.07 MB
Coulomb and exchange operators available. No transformation done.
Memory needed for MP2: 0.00 MW
SCS-MP2 correlation energy: -0.151568280646 (PS= 1.000000 PT= 0.000000)
SCS-MP2 total energy: -76.177785195740
Reference energy -76.026216915094
MP2 singlet pair energy -0.126127623239
MP2 triplet pair energy -0.076321972220
MP2 correlation energy -0.202449595459
!MP2 total energy -76.228666510553
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 20.14 500 610 700 900 950 970 1000 129 960 1100
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200 1210 1080 1600 1650 1300 1700 1380
T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP
2 4 2.79 700 1000 520 2100
GEOM BASIS MCVARS RHF
PROGRAMS * TOTAL MP2 MP2 HF INT
CPU TIMES * 0.20 0.02 0.02 0.02 0.03
REAL TIME * 7.53 SEC
DISK USED * 24.70 MB
**********************************************************************************************************************************
PROGRAM * MP2 (Closed-shell) Authors: C. Hampel, H.-J. Werner, 1991, M. Deegan, P.J. Knowles, 1992
Convergence thresholds: THRVAR = 1.00D-08 THRDEN = 1.00D-06
Number of core orbitals: 1 ( 1 )
Number of closed-shell orbitals: 4 ( 4 )
Number of external orbitals: 19 ( 19 )
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: 76
Number of doubly external CSFs: 2926
Total number of CSFs: 3003
Length of J-op integral file: 0.00 MB
Length of K-op integral file: 0.07 MB
Coulomb and exchange operators available. No transformation done.
Memory needed for MP2: 0.00 MW
SCS-MP2 correlation energy: -0.050881314814 (PS= 0.000000 PT= 1.000000)
SCS-MP2 total energy: -76.077098229908
Reference energy -76.026216915094
MP2 singlet pair energy -0.126127623239
MP2 triplet pair energy -0.076321972220
MP2 correlation energy -0.202449595459
!MP2 total energy -76.228666510553
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 20.14 500 610 700 900 950 970 1000 129 960 1100
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200 1210 1080 1600 1650 1300 1700 1380
T V H0 H01 AOSYM SMH MOLCAS ERIS OPER JKOP
2 4 2.79 700 1000 520 2100
GEOM BASIS MCVARS RHF
PROGRAMS * TOTAL MP2 MP2 MP2 HF INT
CPU TIMES * 0.22 0.02 0.02 0.02 0.02 0.03
REAL TIME * 7.57 SEC
DISK USED * 24.70 MB
**********************************************************************************************************************************
MP2/cc-pVDZ energy= -76.228666510553
MP2 HF-SCF
-76.22866651 -76.02621692
**********************************************************************************************************************************
Molpro calculation terminated
Variable memory released
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