[molpro-user] dipole-quadrupole molecular polarizability tensors
Tatiana Korona
tania at tiger.chem.uw.edu.pl
Wed Jan 5 00:58:07 GMT 2011
Dear Dennis,
Yes, it seems to be an error in the printing part of the HF polarizability
calculation, which has been introduced after 2009.2/PL1051 - I attach two
outputs: the first one from molpro2009.2/PL1051, and the second one - from
molpro2010.2. Note that in the older HF output there is however no mixed
dip-quad part. For the moment (and if sizes of your molecules allow this)
you can use
hf
core,0
{mp2
polar,dm,sm
}
then you get HF and MP2 static polarizabilities of all sorts within the MP2
output.
Best wishes,
Tatiana
On Tue, 4 Jan 2011, Elking, Denny (NIH/NIEHS) [G] wrote:
> Dear Molpro Users/Developers Community,
>
> My question involves calculating dipole-dipole, dipole-quadrupole, quadrupole-quadrupole (and possibly higher order) molecular polarizability tensors.
> As an example, I want to calculate the HF/6-31G* polarizability tensors for water in a Cartesian basis set with its geometry given at the end.
>
> 1) I can get the dipole-dipole polarizability tensor for water using the "polarizability,DM" keyword
> DMX DMY DMZ
> DMX 3.800512 0.953377 0.000000
> DMY 0.953377 3.677339 0.000000
> DMZ 0.000000 0.000000 6.630503
> This result agrees with Cadpac.
> X Y Z
> X 3.80051678 0.95338204 0.00000000
> Y 0.95338204 3.67734383 0.00000000
> Z 0.00000000 0.00000000 6.63050501
>
>
> 2) I can also get the quadrupole-quadrupole polarizability tensor using the "polarizability,SM" keyword
> XX YY ZZ XY XZ YZ
> XX 6.272522 2.751293 4.254370 0.548811 0.000000 0.000000
> YY 2.751293 6.138914 3.993306 0.485337 0.000000 0.000000
> ZZ 4.254371 3.993308 15.545155 2.020682 0.000000 0.000000
> XY 0.548811 0.485337 2.020682 2.216464 0.000000 0.000000
> XZ 0.000000 0.000000 0.000000 0.000000 4.512145 2.372242
> YZ 0.000000 0.000000 0.000000 0.000000 2.372242 4.205661
> I realize this is not in traceless Cartesian form, but that's ok. It can be converted to the traceless Buckingham convention later.
> For reference, Cadpac gives the traceless quadrupole-quadrupole polarizability tensor as
> Quadrupole-quadrupole polarisability in atomic units (bohr**5)
> XX YY ZZ XY XZ YZ
> XX 2.228177 -0.314077 -1.914100 -0.352099 0.000000 0.000000
> YY -0.314077 2.325307 -2.011230 -0.399705 0.000000 0.000000
> ZZ -1.914100 -2.011230 3.925330 0.751804 0.000000 0.000000
> XY -0.352099 -0.399705 0.751804 1.662349 0.000000 0.000000
> XZ 0.000000 0.000000 0.000000 0.000000 3.384112 1.779185
> YZ 0.000000 0.000000 0.000000 0.000000 1.779185 3.154249
>
> 3) However, if I try to calculate the dipole-quadrupole polarizability tensor using the "polarizability,DM,SM" keyword, I get something which is not correct.
> DMX DMY DMZ XY XZ YZ
> DMX 3.800512 0.953377 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> DMY 0.953377 3.677339 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> DMZ 0.000000 0.000000 6.630503 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> XX YY ZZ XY XZ YZ XX
> XX 3.800512 0.953377 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> YY 0.953377 3.677339 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> ZZ 0.000000 0.000000 6.630503 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> XY 0.000000 0.000000 0.000000 6.272522 2.751293 4.254370 0.548811 0.000000 0.000000
> XZ 0.000000 0.000000 0.000000 2.751293 6.138914 3.993306 0.485337 0.000000 0.000000
> YZ 0.000000 0.000000 0.000000 4.254371 3.993308 15.545155 2.020682 0.000000 0.000000
> It appears the order of the the tensor components is mixed up in the output file and/or some components may be missing, i.e. all the dipole-quadrupole components are 0.0.
> For comparison, the dipole-quadrupole polarizability from Cadpac is
> XX YY ZZ XY XZ YZ
> X 1.222188 1.345750 -2.567938 -1.061641 0.000000 0.000000
> Y 1.132216 1.275191 -2.407407 -0.994397 0.000000 0.000000
> Z 0.000000 0.000000 0.000000 0.000000 -4.803013 -4.502759
>
> The keyword "polarizability,DM,SM" may be the wrong syntax for calculating the dipole-quadrupole tensors. On the other hand, if "polarizability,DM,SM" is the correct, syntax, then
> I suspect Molpro calculates the polarizability tensors correctly, but there seems to be a problem in how the values get printed out.
>
> Any help or suggestions is greatly appreciated. Many thanks in advance.
>
>
> Best regards,
> Dennis Elking
>
>
>
>
> ***, water cartesian coordinates (XYZ format)
> memory,1,m
> basis=6-31G*
> CARTESIAN
> geomtyp=xyz
> geometry={
> 3
> WATER CARTESIAN COORDINATES
> O 0.04575896 0.04289840 0.00000000
> H -0.36311204 -0.34041260 0.75865000
> H -0.36311204 -0.34041260 -0.75865000
> }
>
> hf
> polarizability,DM
>
>
>
>
>
>
Dr. Tatiana Korona http://tiger.chem.uw.edu.pl/staff/tania/index.html
Quantum Chemistry Laboratory
University of Warsaw
Pasteura 1, PL-02-093 Warsaw, POLAND
`The man who makes no mistakes does not usually make anything.'
Edward John Phelps (1822-1900)
-------------- next part --------------
Primary working directories : /home/tania/.scratch:/home/tania/.scratch4
Secondary working directories : /home/tania/.scratch4:/home/tania/.scratch
Wavefunction directory : /home/tania/wfu/
Main file repository : /home/tania/.scratch/
ARCHNAME : Linux/x86_64
FC : /opt/pgi/linux86-64/8.0/bin/pgf90
FCVERSION : 8.0
BLASLIB : -L/opt/pgi/linux86-64/8.0/lib -lacml_mv -lacml
id : korona
Nodes nprocs
elf.chem.uw.edu.pl 1
mxmblk=64; mxmbln=64; ncache=16384; mindgm=32; mindgv=32; mindgc=24; mindgl=8; mindgr=4; noblas=0; nroll=2; minvec=7
default implementation of scratch files=df
***,water cartesian coordinates (XYZ format)
memory,1,m
basis=6-31G*
cartesian
geomtyp=xyz
geometry={
3
WATER CARTESIAN COORDINATES
O 0.04575896 0.04289840 0.00000000
H -0.36311204 -0.34041260 0.75865000
H -0.36311204 -0.34041260 -0.75865000
}
{hf
polarizability,DM,SM
}
core,0
{mp2
polar,dm,sm}
Variables initialized (649), CPU time= 0.01 sec
Commands initialized (439), CPU time= 0.01 sec, 473 directives.
Default parameters read. Elapsed time= 0.06 sec
Checking input...
Passed
1
*** PROGRAM SYSTEM MOLPRO ***
Copyright, University College Cardiff Consultants Limited, 2008
Version 2009.2 linked 21 Apr 2010 04:12:37
**********************************************************************************************************************************
LABEL * water cartesian coordinates (XYZ format)
Linux-2.6.18-92.el5/elf.chem.uw.edu.pl(x86_64) 64 bit serial version DATE: 05-Jan-11 TIME: 01:24:23
**********************************************************************************************************************************
Patch level: 1051
**********************************************************************************************************************************
Variable memory set to 1000000 words, buffer space 230000 words
SETTING BASIS = 6-31G*
SETTING GEOMTYP = XYZ
Recomputing integrals since basis changed
Using cartesian basis functions
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
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 O 8.00 0.086471902 0.081066227 0.000000000
2 H 1.00 -0.686182311 -0.643286586 1.433640730
3 H 1.00 -0.686182311 -0.643286586 -1.433640730
Bond lengths in Bohr (Angstrom)
1-2 1.782416133 1-3 1.782416133
(0.943213995) (0.943213995)
Bond angles
2-1-3 107.09011232
NUCLEAR CHARGE: 10
NUMBER OF PRIMITIVE AOS: 36
NUMBER OF SYMMETRY AOS: 36
NUMBER OF CONTRACTIONS: 19 ( 13A' + 6A" )
NUMBER OF CORE ORBITALS: 1 ( 1A' + 0A" )
NUMBER OF VALENCE ORBITALS: 6 ( 4A' + 2A" )
NUCLEAR REPULSION ENERGY 9.32534184
Eigenvalues of metric
1 0.218E-01 0.176E+00 0.279E+00 0.426E+00 0.498E+00 0.667E+00 0.672E+00 0.785E+00
2 0.108E+00 0.184E+00 0.670E+00 0.100E+01 0.114E+01 0.233E+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: 10150. BUFFER LENGTH: 32768
NUMBER OF SEGMENTS: 1 SEGMENT LENGTH: 10150 RECORD LENGTH: 262144
Memory used in sort: 0.31 MW
SORT1 READ 13579. AND WROTE 7215. INTEGRALS IN 1 RECORDS. CPU TIME: 0.00 SEC, REAL TIME: 0.00 SEC
SORT2 READ 7215. AND WROTE 10150. INTEGRALS IN 1 RECORDS. CPU TIME: 0.01 SEC, REAL TIME: 0.01 SEC
FILE SIZES: FILE 1: 2.5 MBYTE, FILE 4: 2.1 MBYTE, TOTAL: 4.6 MBYTE
OPERATOR DM FOR CENTER 0 COORDINATES: 0.000000 0.000000 0.000000
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 19 2.29 500 610 700 900 950 970 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 * 0.24 0.03
REAL TIME * 0.26 SEC
DISK USED * 5.14 MB
**********************************************************************************************************************************
1PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner
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. Full valence occupancy: 5 2
Molecular orbital dump at record 2100.2
Initial alpha occupancy: 4 1
Initial beta occupancy: 4 1
Wave function symmetry: 1
ITERATION DDIFF GRAD ENERGY 2-EL.EN. DIPOLE MOMENTS DIIS
1 0.000D+00 0.000D+00 -75.97225298 77.960215 -0.842980 -0.790282 0.000000 0
2 0.000D+00 0.405D-01 -76.00204165 74.668843 -0.588699 -0.551898 0.000000 1
3 0.329D-01 0.213D-01 -76.01043992 75.999483 -0.633380 -0.593786 0.000000 2
4 0.115D-01 0.232D-02 -76.01063546 75.906923 -0.625441 -0.586342 0.000000 3
5 0.163D-02 0.554D-03 -76.01064825 75.917005 -0.622641 -0.583718 0.000000 4
6 0.524D-03 0.900D-04 -76.01064872 75.917029 -0.622071 -0.583183 0.000000 5
7 0.121D-03 0.130D-04 -76.01064873 75.917022 -0.621974 -0.583092 0.000000 6
8 0.189D-04 0.165D-05 -76.01064873 75.917006 -0.621967 -0.583086 0.000000 5
9 0.193D-05 0.384D-06 -76.01064873 75.917012 -0.621967 -0.583086 0.000000 0
Final occupancy: 4 1
!RHF STATE 1.1 Energy -76.010648726251
Nuclear energy 9.32534184
One-electron energy -123.29449654
Two-electron energy 37.95850597
Virial quotient -1.00180526
!RHF STATE 1.1 Dipole moment -0.62196697 -0.58308557 0.00000000
Dipole moment /Debye -1.58077880 -1.48195862 0.00000000
Starting polarizability calculation
CPHF needed 12 iterations for 3 perturbations. Total CPU time: 0.01 sec
Polarizability
Operator DMX DMY DMZ
DMX 3.800512 0.953377 0.000000
DMY 0.953377 3.677339 0.000000
DMZ 0.000000 0.000000 6.630503
Average 4.702785
CPHF needed 11 iterations for 6 perturbations. Total CPU time: 0.01 sec
Polarizability
Operator XX YY ZZ XY XZ YZ
XX 6.272522 2.751293 4.254370 0.548811 0.000000 0.000000
YY 2.751293 6.138914 3.993306 0.485337 0.000000 0.000000
ZZ 4.254371 3.993308 15.545155 2.020682 0.000000 0.000000
XY 0.548811 0.485337 2.020682 2.216464 0.000000 0.000000
XZ 0.000000 0.000000 0.000000 0.000000 4.512145 2.372242
YZ 0.000000 0.000000 0.000000 0.000000 2.372242 4.205661
Orbital energies:
1.1 2.1 3.1 4.1 5.1 6.1
-20.556160 -1.346920 -0.568249 -0.497864 0.214130 1.132639
1.2 2.2 3.2
-0.719549 0.308011 1.041445
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 21 2.29 500 610 700 900 950 970 1000 129 960 1100
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200 1210 1080 1600 1650 1300 1700 960(1)
T V H0 H01 AOSYM SMH MOLCAS ERIS OPER ABASIS
1700(1)
OPER
2 3 0.29 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL HF INT
CPU TIMES * 0.28 0.04 0.03
REAL TIME * 0.46 SEC
DISK USED * 5.14 MB
**********************************************************************************************************************************
1PROGRAM * 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 closed-shell orbitals: 5 ( 4 1 )
Number of external orbitals: 14 ( 9 5 )
Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Number of N-1 electron functions: 5
Number of N-2 electron functions: 15
Number of singly external CSFs: 41
Number of doubly external CSFs: 1296
Total number of CSFs: 1338
Length of J-op integral file: 0.00 MB
Length of K-op integral file: 0.05 MB
Length of 3-ext integral record: 0.00 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: -0.183024927037 (PS= 1.200000 PT= 0.333333)
SCS-MP2 total energy: -76.193673653288
Reference energy -76.010648726251
Correlated core orbitals: 1.1
Orbital energies: -20.5562
MP2 core-core energy -0.000841828480
MP2 core-valence energy -0.001570625990
MP2 valence correlation energy -0.184817192082
MP2 singlet pair energy -0.115141985123
MP2 triplet pair energy -0.072087661430
MP2 correlation energy -0.187229646553
!MP2 total energy -76.197878372804
KEXT needed 1 integral passes. Memory used: 0.04 MW CPU time: 0.00 sec
MP2 density written to record 4610.4
Starting Coupled-perturbed Hartree-Fock, convergence threshold= 1.0D-06
ITER FOCK DIIS VAR VARC CPU
1 0 1 0.46D-01 0.00D+00 0.00
2 1 1 0.13D-01 0.00D+00 0.00
3 1 2 0.38D-02 0.00D+00 0.01
4 1 3 0.12D-02 0.00D+00 0.01
5 1 4 0.21D-03 0.00D+00 0.01
6 1 5 0.43D-04 0.00D+00 0.01
7 1 6 0.60D-05 0.00D+00 0.01
8 1 6 0.14D-05 0.00D+00 0.01
9 1 6 0.14D-06 0.00D+00 0.01
CPHF convergence reached in 8 macroiterations and 0 microiterations. Accuracy: 1.4385D-07
CPHF solution written to record 4661.4
Dipole moments (unrelaxed): -0.61964629 -0.58090997 0.00000000
Orbital relaxation contribution: 0.00743713 0.00697220 0.00000000
!MP2 dipole moments: -0.61220917 -0.57393777 0.00000000
CPU-time for density and lagrangian: 0.00 sec
CPU-time for coupled-perturbed hartree-fock: 0.01 sec
PROGRAM * POLARIZABILITY Authors: K. Pflueger and H.-J. Werner, 2003
Local implementation by K. Pflueger, 2007
Starting CPHF iterations, Threshold= 0.10D-05
CPHF iterations for 9 perturbations converged in 11 iterations
CPHF solution written to record 4570.4
Calculating first order MP2 response density
Computing the perturbed MP2 amplitudes
Starting CPHF iterations, Threshold= 0.10D-05
CPHF iterations for 9 perturbations converged in 10 iterations
SCF polarizabilities
DMX DMY DMZ
DMX 3.800512 0.953377 0.000000
DMY 0.953377 3.677339 0.000000
DMZ 0.000000 0.000000 6.630503
Average 4.702784
MP2 polarizabilities
DMX DMY DMZ
DMX 3.904360 0.984462 0.000000
DMY 0.984462 3.777171 0.000000
DMZ 0.000000 0.000000 6.643315
Average 4.774949
SCF 2nd order properties
DMX DMY XX YY ZZ
DMX 3.800512 0.953377 -0.685798 -0.603424 -3.212544
XY DMZ XZ YZ
DMX -0.707758 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
DMY 0.953377 3.677339 -0.651973 -0.556656 -3.011716
XY DMZ XZ YZ
DMY -0.662929 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
XX -0.685799 -0.651973 6.272522 2.751293 4.254370
XY DMZ XZ YZ
XX 0.548811 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
YY -0.603424 -0.556656 2.751293 6.138914 3.993307
XY DMZ XZ YZ
YY 0.485337 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
ZZ -3.212544 -3.011717 4.254370 3.993306 15.545157
XY DMZ XZ YZ
ZZ 2.020682 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
XY -0.707759 -0.662930 0.548811 0.485337 2.020682
XY DMZ XZ YZ
XY 2.216464 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
DMZ 0.000000 0.000000 0.000000 0.000000 0.000000
XY DMZ XZ YZ
DMZ 0.000000 6.630503 -3.202004 -3.001835
DMX DMY XX YY ZZ
XZ 0.000000 0.000000 0.000000 0.000000 0.000000
XY DMZ XZ YZ
XZ 0.000000 -3.202004 4.512145 2.372242
DMX DMY XX YY ZZ
YZ 0.000000 0.000000 0.000000 0.000000 0.000000
XY DMZ XZ YZ
YZ 0.000000 -3.001835 2.372242 4.205662
MP2 2nd order properties
DMX DMY XX YY ZZ
DMX 3.904360 0.984462 -0.839650 -0.727340 -3.425993
XY DMZ XZ YZ
DMX -0.722159 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
DMY 0.984462 3.777171 -0.768190 -0.700842 -3.211822
XY DMZ XZ YZ
DMY -0.678239 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
XX -0.839650 -0.768190 6.285260 2.975345 4.724162
XY DMZ XZ YZ
XX 0.642649 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
YY -0.727340 -0.700842 2.975345 6.127377 4.452774
XY DMZ XZ YZ
YY 0.579397 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
ZZ -3.425993 -3.211822 4.724162 4.452774 16.347268
XY DMZ XZ YZ
ZZ 2.100596 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
XY -0.722159 -0.678240 0.642649 0.579396 2.100596
XY DMZ XZ YZ
XY 2.103034 0.000000 0.000000 0.000000
DMX DMY XX YY ZZ
DMZ 0.000000 0.000000 0.000000 0.000000 0.000000
XY DMZ XZ YZ
DMZ 0.000000 6.643315 -3.215373 -3.014368
DMX DMY XX YY ZZ
XZ 0.000000 0.000000 0.000000 0.000000 0.000000
XY DMZ XZ YZ
XZ 0.000000 -3.215373 4.509422 2.405089
DMX DMY XX YY ZZ
YZ 0.000000 0.000000 0.000000 0.000000 0.000000
XY DMZ XZ YZ
YZ 0.000000 -3.014368 2.405089 4.198695
Total CPU-time for polarizabilities: 0.05 sec
CPU-time for CPHF iterations: 0.01 sec
CPU-time for perturbed MP2 amplitudes and density: 0.00 sec
CPU-time for left sides of first order Z-CPHF equations: 0.03 sec
CPU-time for Z-CPHF iterations: 0.01 sec
**********************************************************************************************************************************
DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
1 22 2.37 500 610 700 900 950 970 1000 129 960 1100
VAR BASINP GEOM SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
1400 1410 1200 1210 1080 1600 1650 1300 1700 960(1)
T V H0 H01 AOSYM SMH MOLCAS ERIS OPER ABASIS
1700(1) 1380
OPER JKOP
2 3 0.29 700 1000 2100
GEOM BASIS RHF
PROGRAMS * TOTAL MP2 HF INT
CPU TIMES * 0.41 0.11 0.04 0.03
REAL TIME * 0.91 SEC
DISK USED * 5.14 MB
**********************************************************************************************************************************
MP2 HF-SCF
-76.19787837 -76.01064873
**********************************************************************************************************************************
Variable memory released
-------------- next part --------------
A non-text attachment was scrubbed...
Name: my_dip_quad_10.out
Type: application/octet-stream
Size: 25432 bytes
Desc:
URL: <http://www.molpro.net/pipermail/molpro-user/attachments/20110105/ce8b3c06/attachment.obj>
More information about the Molpro-user
mailing list