[molpro-user] Why the MCSCF energy is lower than Full-CI?
cong.wang
cong.wang at helsinki.fi
Sat Feb 13 15:28:05 GMT 2010
Dear everyone,
Hello,
Excuse me, I did a HF, CASSCF(4,8), and Full-CI calculations for
H4 square molecule with 6-31G basis set on molpro 2009. The CASSCF
energy is lower than FCI by 0.02 a.u., what would be the explanation
for that? Should the CASSCF(4,8) and FCI be equivalent in this case?
Here are the input and output files
Thank you very much in advance
Best regards
Sincerely,
Cong Wang
Ph. D. Student
Department of Chemistry
Laboratory for Instruction in Swedish
University of Helsinki
A.I. Virtanens plats 1
P.O. Box 55
FI-00014 University of Helsinki
FINLAND
***,h4 !A title
symmetry,nosym
geomtyp=xyz
geometry={
4
title
H 0. 0. 0.
H 0. 0. 0.5
H 0. 0.5 0.
H 0. 0.5 0.5
}
basis={
!
! HYDROGEN (4s) -> [2s]
s, H , 18.7311370, 2.8253937, 0.6401217, 0.1612778
c, 1.3, 0.03349460, 0.23472695, 0.81375733
c, 4.4, 1
}
hf !closed-shell scf
{fci;occ,8;core,0;wf,4,1}
{multi;occ,8}
*******************
Here is the output file
***,h4
symmetry,nosym
geomtyp=xyz
geometry={
4
title
H 0. 0. 0.
H 0. 0. 0.5
H 0. 0.5 0.
H 0. 0.5 0.5
}
basis={
!
! HYDROGEN (4s) -> [2s]
s, H , 18.7311370, 2.8253937, 0.6401217, 0.1612778
c, 1.3, 0.03349460, 0.23472695, 0.81375733
c, 4.4, 1
}
hf
!closed-shell scf
{fci;occ,8;core,0;wf,4,1}
{multi;occ,8}
Variables initialized (631), CPU time= 0.02 sec
Commands initialized (426), CPU time= 0.03 sec, 469 directives.
Default parameters read. Elapsed time= 0.12 sec
Checking input...
Passed
1
*** PROGRAM SYSTEM MOLPRO ***
Copyright, University College Cardiff
Consultants Limited, 2008
Version 2009.1 linked 11 Dec 2009 10:14:28
**********************************************************************************************************************************
LABEL * h4
Linux-2.6.9-67.9hp.8sp.XCsmp/c18(x86_64) 64 bit mpp version
DATE: 13-Feb-10 TIME: 17:19:36
**********************************************************************************************************************************
Patch level: 26
**********************************************************************************************************************************
Variable memory set to 8000000 words, buffer space 230000 words
SETTING GEOMTYP = XYZ
ZSYMEL=NOSYM
SETTING BASIS = USERDEF
Recomputing integrals since basis changed
Using spherical harmonics
1PROGRAM * 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 0.000000000 0.000000000
2 H 1.00 0.000000000 0.000000000 0.944863066
3 H 1.00 0.000000000 0.944863066 0.000000000
4 H 1.00 0.000000000 0.944863066 0.944863066
Bond lengths in Bohr (Angstrom)
1-2 0.944863066 1-3 0.944863066 1-4 1.336238162 2-3
1.336238162 2-4 0.944863066
(0.500000000) (0.500000000) (0.707106781)
(0.707106781) (0.500000000)
3-4 0.944863066
(0.500000000)
Bond angles
1-2-3 45.00000000 1-2-4 90.00000000 1-3-2 45.00000000
1-3-4 90.00000000
1-4-2 45.00000000 1-4-3 45.00000000 2-1-3 90.00000000
2-1-4 45.00000000
2-3-4 45.00000000 2-4-3 90.00000000 3-1-4 45.00000000
3-2-4 45.00000000
NUCLEAR CHARGE: 4
NUMBER OF PRIMITIVE AOS: 16
NUMBER OF SYMMETRY AOS: 16
NUMBER OF CONTRACTIONS: 8 ( 8A )
NUMBER OF CORE ORBITALS: 0 ( 0A )
NUMBER OF VALENCE ORBITALS: 4 ( 4A )
NUCLEAR REPULSION ENERGY 5.73015684
Eigenvalues of metric
1 0.424E-02 0.895E-01 0.895E-01 0.116E+00 0.559E+00 0.559E+00
0.901E+00 0.568E+01
Contracted 2-electron integrals neglected if value below 1.0E-11
AO integral compression algorithm 1 Integral accuracy 1.0E-11
0.524 MB (compressed) written to integral file (100.0%)
Node minimum: 0.262 MB, node maximum: 0.262 MB
NUMBER OF SORTED TWO-ELECTRON INTEGRALS: 342. BUFFER LENGTH: 32768
NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 342 RECORD LENGTH: 524288
Memory used in sort: 0.56 MW
SORT1 READ 1040. AND WROTE 342. INTEGRALS IN 1
RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.03 SEC
SORT2 READ 666. AND WROTE 666. INTEGRALS IN 2
RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.01 SEC
Node minimum: 324. Node maximum: 342. integrals
OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000
0.000000
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 18 2.24 500 610 700
900 950 970 1000 129 960 1100
VAR BASINP GEOM
SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200
1210 1080 1600 1650 1700
T V H0
H01 AOSYM SMH MOLCAS OPER
PROGRAMS * TOTAL INT
CPU TIMES * 0.25 0.04
REAL TIME * 0.86 SEC
DISK USED * 8.40 MB
GA USED * 0.00 MB (max) 0.00 MB (current)
**********************************************************************************************************************************
1PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner
NUMBER OF ELECTRONS: 2+ 2- 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: 2
Molecular orbital dump at record 2100.2
ITERATION DDIFF GRAD ENERGY 2-EL.EN.
DIPOLE MOMENTS DIIS
1 0.000E+00 0.000E+00 -1.01850516 6.476015
0.000000 0.000000 0.000000 0
2 0.000E+00 0.587E-01 -1.05651369 6.784778
0.000000 0.000000 0.000000 1
3 0.896E-01 0.923E-02 -1.05796300 6.767464
0.000000 0.000000 0.000000 2
4 0.378E-01 0.216E-02 -1.05826410 6.761665
0.000000 0.000000 0.000000 3
5 0.253E-01 0.141E-02 -1.05951712 6.765025
0.000000 0.000000 0.000000 4
6 0.139E+00 0.112E-02 -1.06074940 6.788974
0.000000 0.000000 0.000000 5
7 0.401E+00 0.221E-02 -1.06066222 6.794301
0.000000 0.000000 0.000000 6
8 0.231E-01 0.273E-02 -1.06088156 6.765436
0.000000 0.000000 0.000000 6
9 0.111E+00 0.912E-04 -1.06088511 6.767986
0.000000 0.000000 0.000000 7
10 0.299E-01 0.198E-03 -1.06088680 6.766019
0.000000 0.000000 0.000000 7
11 0.862E-02 0.819E-05 -1.06088680 6.765931
0.000000 0.000000 0.000000 7
12 0.598E-03 0.458E-06 -1.06088680 6.765936
0.000000 0.000000 0.000000 4
13 0.113E-04 0.833E-08 -1.06088680 6.765936
0.000000 0.000000 0.000000 3
14 0.816E-06 0.145E-08 -1.06088680 6.765936
0.000000 0.000000 0.000000 0
Final occupancy: 2
!RHF STATE 1.1 Energy -1.060886803967
Nuclear energy 5.73015684
One-electron energy -10.17401176
Two-electron energy 3.38296811
Virial quotient -0.30535441
!RHF STATE 1.1 Dipole moment 0.00000000 0.00000000 0.00000000
Dipole moment /Debye 0.00000000 0.00000000 0.00000000
Orbital energies:
1.1 2.1 3.1 4.1
-1.484903 -0.219135 0.118997 0.347029
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 2.24 500 610 700
900 950 970 1000 129 960 1100
VAR BASINP GEOM
SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200
1210 1080 1600 1650 1700 960(1)
T V H0
H01 AOSYM SMH MOLCAS OPER ABASIS
2 3 0.30 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL HF INT
CPU TIMES * 0.27 0.01 0.04
REAL TIME * 0.93 SEC
DISK USED * 14.05 MB
SF USED * 0.00 MB
GA USED * 0.00 MB (max) 0.00 MB (current)
**********************************************************************************************************************************
1PROGRAM * FCI (Full CI) Author: P.J. Knowles, 1984
*** Initialisation ***
Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Frozen orbitals: 0 ( 0 0 0 0 0 0 0 0)
Active orbitals: 8 ( 8 0 0 0 0 0 0 0)
Active electrons: 4
Spin quantum number: 0.0
Orbital pairs: 36 0 0 0 0
0 0 0
Strings: 28 0 0 0 0
0 0 0
28 0 0 0 0
0 0 0
Determinants: 784 0 0 0 0
0 0 0
Load integrals 0.3 sec
Transform integrals 0.3 sec
Storage for integrals: 1432
Remaining memory: 7998276
Core energy: 5.73015684
Run Hamiltonian processor DAVIDSON
Symmetry: 1
Trial vector: 0.00
Result vector: 0.00
Maximum iterations: 90
Convergence threshold: 0.0000100
RHS vector: 0.00
Hamiltonian shift: 0.0000000
Output threshold: 0.0500000
Options: 0
Number of roots: 1
0Hamiltonian diagonaliser entered at time 0.29
0Initial configuration generated:
2 0.7071068 -1.0926897
29 0.7071068 -1.0926897
It Tr CPU Convergence Energy Pop dE(next)
1 1 0.3 1.00000000 -1.06497453
+ 0.07 -0.04894565 -0.04845022
2 1 0.3 0.16243432 -1.10830923
+ 0.13 -0.00201200 -0.00194720
3 1 0.3 0.03189825 -1.11019693
+ 0.15 -0.00009890 -0.00009653
4 1 0.3 0.00619425 -1.11029626
+ 0.11 -0.00000431 -0.00000415
5 1 0.3 0.00113560 -1.11030039
+ 0.13 -0.00000024 -0.00000024
6 1 0.3 0.00026966 -1.11030063
+ 0.13 -0.00000001 -0.00000001
7 1 0.3 0.00006100 -1.11030064
+ 0.14 0.00000000 0.00000000
8 1 0.3 0.00001235 -1.11030064
+ 0.13 0.00000000 0.00000000
9 1 0.3 0.00000273 -1.11030064
RESULTS FOR STATE 1.1
=====================
Correlation energy -0.045326113978
!FCI STATE 1.1 Energy -1.110300643555
CI Vector (threshold= 0.500E-01)
0.697298777599 1 2 1 3
0.059500107090 1 2 1 7
0.697298777599 1 3 1 2
0.069818256450 1 4 1 5
0.069818256450 1 5 1 4
0.059500107090 1 7 1 2
/EOF
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 2.24 500 610 700
900 950 970 1000 129 960 1100
VAR BASINP GEOM
SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200
1210 1080 1600 1650 1700 960(1)
T V H0
H01 AOSYM SMH MOLCAS OPER ABASIS
2 3 0.30 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL FCI HF INT
CPU TIMES * 0.28 0.02 0.01 0.04
REAL TIME * 1.00 SEC
DISK USED * 14.05 MB
SF USED * 0.12 MB
GA USED * 0.00 MB (max) 0.00 MB (current)
**********************************************************************************************************************************
1PROGRAM * MULTI (Direct Multiconfiguration SCF) Authors: P.J.
Knowles, H.-J. Werner (1984) S.T. Elbert (1988)
Number of active orbitals: 8 ( 8 )
Number of external orbitals: 0 ( 0 )
State symmetry 1
Number of electrons: 4 Spin symmetry=Singlet Space symmetry=1
Number of states: 1
Number of CSFs: 336 (784 determinants, 784 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: 0 ( 0 Core/Active 0
Core/Virtual 0 Active/Active 0 Active/Virtual)
Total number of variables: 784
ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE
GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME
1 6 13 0 -1.13054659 -1.13054659 0.00000000
0.00000000 0.00000000 0.00000001 0.00E+00 0.04
** WVFN **** CONVERGENCE REACHED, FINAL GRADIENT: 0.00E+00
First order charge density matrix for state 1.1 saved on record
2140.2 (density set 1)
Results for state 1.1
=====================
!MCSCF STATE 1.1 Energy -1.130546590250
Nuclear energy 5.73015684
Kinetic energy 3.55743771
One electron energy -10.16319936
Two electron energy 3.30249592
Virial ratio 1.31779800
!MCSCF STATE 1.1 Dipole moment 0.00000000 0.00000000 0.00000000
Dipole moment /Debye 0.00000000 0.00000000 0.00000000
Natural orbital dump at molpro section 2140.2
(Orbital set 2)
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 20 2.27 500 610 700
900 950 970 1000 129 960 1100
VAR BASINP GEOM
SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200
1210 1080 1600 1650 1700 960(1) 1380
T V H0
H01 AOSYM SMH MOLCAS OPER ABASIS JKOP
2 4 0.34 700 1000 2100 2140
GEOM BASIS RHF MCSCF
PROGRAMS * TOTAL MULTI FCI HF INT
CPU TIMES * 0.34 0.05 0.02 0.01 0.04
REAL TIME * 1.61 SEC
DISK USED * 14.05 MB
SF USED * 3.21 MB
GA USED * 0.00 MB (max) 0.00 MB (current)
**********************************************************************************************************************************
MULTI FCI HF-SCF
-1.13054659 -1.11030064 -1.06088680
**********************************************************************************************************************************
Variable memory released
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