[molpro-user] Analytic geometry optimization with density-fitting CASSCF by RS2 did not work
Werner Győrffy
gyorffy at theochem.uni-stuttgart.de
Wed Sep 21 09:58:56 CEST 2016
Dear MJ Wu,
You have performed a transition state search (optg,root=2) in your
calculation, which requires calculating the Hessian. The Hessian can be
obtained by computing second derivatives of the energy with respect to
nuclear displacements. The gradients, which are first derivatives of the
energy, were calculated by using analytical gradients. The Hessian
however was calculated by using numerical first derivatives of the
analytical gradients. Currently, this is the only way in Molpro to
compute the DF-CASSCF Hessian.
Regards,
Werner.
On 09/19/2016 07:30 PM, Kenny W wrote:
> Dear Molpro Experts,
>
> I tried to do geometry optimization at df-CASSCF level, and wished the
> job to run using analytic gradient via df-RS2 with "noexc"
> keyword:(reference: http://www.molpro.net/pipermail/molpro-user/2012-October/005092.html
> )
> However, the geometry optimization still proceeded with numerical
> gradient. Here is my input:
>
> ***,df-CAS(12,12) optimization
> memory,15000,m
>
> cartesian
> basis=6-31G*
> geomtyp=xyz
> geometry={
> 39
> TS optimization
> C -4.85773400 0.51429900 0.42945500
> .... atomic coordinates follows ...
> H 0.73880900 2.27415000 -0.56530600
> }
> ! orbital from previous df-CAS/6-31G*
> {matrop
> read,oldorbitals,file=radical_df4.orb
> save,oldorbitals,2140.2,orbitals}
>
> {df-multi,DF_BASIS=vdz/JKFIT
> start,2140.2
> close,76
> occ,88
> wf,164,1,0
> natorb,ci,print
> orbital,2141.2
> maxiter,39
> }
>
> ! change basis to VDZ with density fitting
> basis={
> default,vdz
> set,fit ! defines a basis set called fit
> default,vdz/JKFIT} ! here uses slash in the basis name
> {cfit,basis=fit} ! defines the DF basis set
> spherical
>
> {df-multi
> start,2141.2
> close,76
> occ,88
> wf,164,1,0
> natorb,ci,print
> orbital,2142.2
> maxiter,39
> }
>
> ! df-CAS analytic gradient using df-RS2 with keyword noexc
> {df-RS2,thrden=1.0d-11,thrvar=1.0d-11,maxit=100,maxiti=100
> core,75 ! this should be redundant with noexc
> occ,88
> close,76
> noexc; ! this is just for analytic grad
> wf,164,1,0;
> state,1,1
> orbit,2142.2
> }
>
> optg,root=2 ! optimize for transition state
>
> Everything went fine until df-RS2 finished, and the RSPT2 energy indeed
> equals to the CASSCF reference energy. But while starting geometry
> optimization, I found in the output file that the calculation still used
> numeric gradient.
>
> May I know what went wrong with the input file? The tail of the output
> file follows. Thank you very much for your help!
>
> Sincerely,
> MJ Wu
>
> *Reference energy -1293.32140467*
> Nuclear energy 1881.75751251
> Kinetic energy 1292.96788162
> One electron energy -5511.10187574
> Two electron energy 2336.02295856
> Virial quotient -1.00027342
> Correlation energy 0.00000000
> *!RSPT2 STATE 1.1 Energy -1293.32140466*6142
>
> !RSPT2 STATE 1.1 Dipole moment -1.75999116 -0.81167791
> 0.50501499
> Dipole moment /Debye -4.47315833 -2.06294434
> 1.28353600
>
> Hylleraas correlation energy: 0.00000000
> *Total energy: -1293.32140467*
>
> Solving MCSCF z-vector equations for state 1.1, requested accuracy=
> 0.10D-05
> Convergence reached in 4 iterations ( 4 expansion vectors),
> accuracy= 0.65D-06
>
> Reference dipole moments: -1.75999116 -0.81167791
> 0.50501499
> !RSPT2 dipole moments (ED): -1.76000654 -0.81168150
> 0.50501620
>
> RSPT2 Gradient info saved on record 5200.1
>
> CPU-time for rhs: 703.84 sec
> CPU-time for cpmcscf: 3765.26 sec
> CPU-time for densities: 2.35 sec
>
>
> **********************************************************************************************************************************
> DATASETS * FILE NREC LENGTH (MB) RECORD NAMES
> 1 25 7557.78 500 610 700 900
> 950 970 1001 129 960 1100
> VAR BASINP GEOM
> SYMINP ZMAT AOBASIS BASIS P2S ABASIS S
> 1400 1410 1200 1210
> 1080 1600 1650 1700 1380 5200
> T V H0 H01
> AOSYM SMH MOLCAS OPER JKOP RS2GRAD
> 5210 7009 90002 90003
> 7005
> RS2GRAD ITF ITF
>
> 2 7 18.73 700 1000 520 2140
> 2141 1001 2142
> GEOM BASIS MCVARS
> MATROP MCSCF BASIS MCSCF
>
> PROGRAMS * TOTAL RS2 MULTI INT MULTI
> MATROP INT
> CPU TIMES * 42786.30 5427.08 21523.68 13.74 15548.16
> 2.63 266.23
> REAL TIME * 4057.84 SEC
> DISK USED * 78.76 GB
> **********************************************************************************************************************************
>
>
> PROGRAM * OPT (Geometry optimization) Authors: F. Eckert and H.-J.
> Werner
>
>
> Geometry optimization using default procedure for command DF-RS2
>
> Geometry written to block 1 of record 700
>
> * Generated 111 symmetrical displacements*
>
> * Numerically approximating hessian using forward gradient differences*
>
> Task list generated. Total number of displacements: 111
>
> 11 tasks completed, CPU=3d 16h 28m 23s Elapsed=9h 25m 6s
> 22 tasks completed, CPU=7d 2h 25m 20s Elapsed=17h 49m 50s
>
>
>
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