[molpro-user] Why the MCSCF energy is lower than Full-CI?
cong.wang
cong.wang at helsinki.fi
Mon Feb 15 12:45:22 GMT 2010
Dear Professor Knowles and Peterson,
Many thanks for your help. I tried to simply write FCI, without
assigning occ,8; or switch on the symmetry. In molpro 2009.1 (I don't
have version 2009.2 at this moment) they still provide the same
energies as before. Putting FCI after MCSCF indeed obtain the same
result. The output file is in the end of this letter.
Best regards
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
!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}
fci
{multi;occ,8}
{fci;occ,8;core,0;wf,4,1}
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/c51(x86_64) 64 bit mpp version
DATE: 15-Feb-10 TIME: 14:32:57
**********************************************************************************************************************************
Patch level: 26
**********************************************************************************************************************************
SETTING GEOMTYP = XYZ
Variable memory set to 8000000 words, buffer space 230000 words
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 Cs
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' + 0A" )
NUMBER OF CORE ORBITALS: 0 ( 0A' + 0A" )
NUMBER OF VALENCE ORBITALS: 4 ( 4A' + 0A" )
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: 0.02 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 0.03
REAL TIME * 0.42 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 -1.01765285 6.477720
0.000000 0.000000 0.000000 0
2 0.000E+00 0.586E-01 -1.05564703 6.783869
0.000000 0.000000 0.000000 1
3 0.887E-01 0.930E-02 -1.05713903 6.766115
0.000000 0.000000 0.000000 2
4 0.386E-01 0.221E-02 -1.05747179 6.760430
0.000000 0.000000 0.000000 3
5 0.261E-01 0.151E-02 -1.05851596 6.762637
0.000000 0.000000 0.000000 4
6 0.100E+00 0.136E-02 -1.06001733 6.821965
0.000000 0.000000 0.000000 5
7 0.611E+00 0.542E-02 -1.05989755 6.825670
0.000000 0.000000 0.000000 6
8 0.118E-01 0.579E-02 -1.06081446 6.763077
0.000000 0.000000 0.000000 6
9 0.262E+00 0.377E-03 -1.06086390 6.773574
0.000000 0.000000 0.000000 7
10 0.110E+00 0.739E-03 -1.06088668 6.766407
0.000000 0.000000 0.000000 8
11 0.310E-01 0.458E-04 -1.06088680 6.765938
0.000000 0.000000 0.000000 7
12 0.259E-02 0.323E-06 -1.06088680 6.765936
0.000000 0.000000 0.000000 4
13 0.682E-04 0.694E-07 -1.06088680 6.765936
0.000000 0.000000 0.000000 3
14 0.852E-05 0.107E-07 -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 * 0.29 0.03 0.03
REAL TIME * 0.49 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 0.31
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 -0.045326113954
!FCI STATE 1.1 Energy -1.110300643555
CI Vector (threshold= 0.500E-01)
0.697298777620 1 2 1 3
0.059500107021 1 2 1 7
0.697298777620 1 3 1 2
0.069818256453 1 4 1 5
0.069818256453 1 5 1 4
0.059500107021 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 * 0.30 0.01 0.03 0.03
REAL TIME * 0.55 SEC
DISK USED * 14.05 MB
SF USED * 0.12 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 0.33
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 -0.045326113954
!FCI STATE 1.1 Energy -1.110300643555
CI Vector (threshold= 0.500E-01)
0.697298777620 1 2 1 3
0.059500107021 1 2 1 7
0.697298777620 1 3 1 2
0.069818256453 1 4 1 5
0.069818256453 1 5 1 4
0.059500107021 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 FCI HF INT
CPU TIMES * 0.31 0.01 0.01 0.03 0.03
REAL TIME * 1.09 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 0.03
** 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 FCI HF INT
CPU TIMES * 0.36 0.04 0.01 0.01 0.03 0.03
REAL TIME * 1.24 SEC
DISK USED * 14.05 MB
SF USED * 3.21 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 2140.2 Type=MCSCF/NATURAL (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 0.4 sec
Transform integrals 0.4 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 0.39
0Initial configuration generated:
2 0.7071068 -1.1009045
29 0.7071068 -1.1009045
It Tr CPU Convergence Energy Pop dE(next)
1 1 0.4 1.00000000 -1.07032368
+ 0.08 -0.03864101 -0.03852237
2 1 0.4 0.12076255 -1.10676691
+ 0.10 -0.00205959 -0.00198136
3 1 0.4 0.03774750 -1.10928734
+ 0.09 -0.00073736 -0.00070602
4 1 0.4 0.02181568 -1.11015881
+ 0.14 -0.00014310 -0.00013870
5 1 0.4 0.00703360 -1.11028947
+ 0.17 -0.00001109 -0.00001070
6 1 0.4 0.00207125 -1.11029977
+ 0.15 -0.00000084 -0.00000077
7 1 0.4 0.00067733 -1.11030050
+ 0.21 -0.00000015 -0.00000014
8 1 0.4 0.00043124 -1.11030063
+ 0.17 -0.00000003 -0.00000002
9 1 0.4 0.00008292 -1.11030066
+ 0.12 -0.00000001 -0.00000001
10 1 0.4 0.00145189 -1.11030069
+ 0.19 -0.00000008 -0.00000007
11 1 0.4 0.24948370 -1.12738049
+ 0.19 -0.00313285 -0.00287901
12 1 0.4 0.03055107 -1.13019398
+ 0.24 -0.00033069 -0.00031087
13 1 0.4 0.00944133 -1.13051443
+ 0.20 -0.00002782 -0.00002586
14 1 0.4 0.00299820 -1.13054151
+ 0.20 -0.00000426 -0.00000398
15 1 0.4 0.00115029 -1.13054583
+ 0.21 -0.00000065 -0.00000061
16 1 0.4 0.00044870 -1.13054650
+ 0.21 -0.00000008 -0.00000008
17 1 0.4 0.00016416 -1.13054658
+ 0.23 -0.00000001 -0.00000001
18 1 0.4 0.00004598 -1.13054659
+ 0.24 0.00000000 0.00000000
19 1 0.4 0.00001205 -1.13054659
+ 0.24 0.00000000 0.00000000
20 1 0.4 0.00000475 -1.13054659
RESULTS FOR STATE 1.1
=====================
Correlation energy -0.060222910110
!FCI STATE 1.1 Energy -1.130546590243
CI Vector (threshold= 0.500E-01)
0.702394487175 1 2 1 2
-0.702394486902 1 3 1 3
/EOF
**********************************************************************************************************************************
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 FCI MULTI FCI FCI
HF INT
CPU TIMES * 0.39 0.02 0.04 0.01 0.01
0.03 0.03
REAL TIME * 1.33 SEC
DISK USED * 14.05 MB
SF USED * 3.21 MB
GA USED * 0.00 MB (max) 0.00 MB (current)
**********************************************************************************************************************************
FCI MULTI FCI FCI HF-SCF
-1.13054659 -1.13054659 -1.11030064 -1.11030064 -1.06088680
**********************************************************************************************************************************
Variable memory released
On Sun, Feb 14, 2010 at 3:50 PM, Peter Knowles <KnowlesPJ at cardiff.ac.uk> wrote:
> In this example, you are a victim of the relatively primitive initial
> wavefunction guess in the FCI code. It picks the lowest energy
> determinant, which happens to be an open-shell configuration that is
> of different symmetry to the ground state. The MCSCF code uses a
> different algorithm and correctly finds the singlet A_g state.
> Everything comes right if you either remove the 'nosym' card, or
> displace the geometry very slightly to break the symmetry. In either
> case, you'll get the same energy from both programs, although if you
> were to do this in a bigger basis set it would be necessary to run fci
> after mcscf in order to use the same orbitals.
> Peter
> On 13 Feb 2010, at 15:28, cong.wang wrote:
>
>> 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
>> _______________________________________________
>> Molpro-user mailing list
>> Molpro-user at molpro.net
>> http://www.molpro.net/mailman/listinfo/molpro-user
>
> --
> Prof. Peter J. Knowles
> School of Chemistry, Cardiff University, Main Building, Park Place,
> Cardiff CF10 3AT, UK
> Email KnowlesPJ at Cardiff.ac.uk
> WWW http://www.cardiff.ac.uk/chemy/contactsandpeople/academicstaff/knowles.html
> Secretary: Alison Thompson, ThompsonAF at Cardiff.ac.uk Telephone +44 29
> 208 74805
>
>
>
>
> _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user
>
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