[molpro-user] mcscf problems

Valentina Cantatore valecantatore at gmail.com
Tue Dec 4 10:24:49 GMT 2012


Dear molpro users,
I am a new trial user of Molpro. I was performing an mcscf optimization for a deformed structure of the azobenzene molecule with the 2010.1 version of the code. The input that I used is:
***TAB (C2)
memory,200, m
gprint,basis,orbitals,civector
file,2,rot1814.sp.optg.wfn
punch,rot1814.optg.pun,new

NXX3      =     0.61995528D+00    ANG
CN5       =     0.14279844D+01    ANG
CNXX5     =     0.11505652D+03    DEGREE
DIH5      =     45.0
CC6       =     0.13908971D+01    ANG
CCN6      =     0.12443263D+03    DEGREE
DIH6      =    -0.14065092D+00    DEGREE
CC7       =     0.13844965D+01    ANG
CCN7      =     0.11542246D+03    DEGREE
DIH7      =    -0.18013427D+03    DEGREE
HC8       =     0.10742867D+01    ANG
HCC8      =     0.11878147D+03    DEGREE
DIH8      =     0.18000000D+03    DEGREE
HC9       =     0.10720031D+01    ANG
HCC9      =     0.11970712D+03    DEGREE
DIH9      =     0.18000000D+03    DEGREE
CC10      =     0.13817785D+01    ANG
CCC10     =     0.11946866D+03    DEGREE
DIH10     =     0.26434144D-14    DEGREE
CC11      =     0.13865300D+01    ANG
CCC11     =     0.12018910D+03    DEGREE
DIH11     =    -0.39103991D-14    DEGREE
HC12      =     0.10749358D+01    ANG
HCC12     =     0.11992410D+03    DEGREE
DIH12     =     0.18000000D+03    DEGREE
HC13      =     0.10751730D+01    ANG
HCC13     =     0.11963628D+03    DEGREE
DIH13     =    -0.18000000D+03    DEGREE
CC14      =     0.13894673D+01    ANG
CCC14     =     0.12046391D+03    DEGREE
DIH14     =     0.00000000D+00    DEGREE
HC15      =     0.10752112D+01    ANG
HCC15     =     0.11996380D+03    DEGREE
DIH15     =    -0.18000000D+03    DEGREE

Geometry={
ang
 q
 q,   1, 1.00
 n,   1, nxx3,       2,   90.000
 n,   1, nxx3,       3,  180.000,     2,  90.000
 c,   3, cn5 ,       1, cnxx5   ,     2, dih5
 c,   5, cc6 ,       3, ccn6    ,     1, dih6
 c,   5, cc7 ,       3, ccn7    ,     1, dih7
 h,   7, hc8 ,       5, hcc8    ,     6, dih8
 h,   6, hc9 ,       5, hcc9    ,     7, dih9
 c,   6, cc10,       5, ccc10   ,     7, dih10
 c,   7, cc11,       5, ccc11   ,     6, dih11
 h,  11, hc12,       7, hcc12   ,     5, dih12
 h,  10, hc13,       6, hcc13   ,     5, dih13
 c,  10, cc14,       6, ccc14   ,     5, dih14
 h,  14, hc15,      10, hcc15   ,     6, dih15
 c,   4, cn5 ,       1, cnxx5   ,     2, dih5
 c,  16, cc6 ,       4, ccn6    ,     1, dih6
 c,  16, cc7 ,       4, ccn7    ,     1, dih7
 h,  18, hc8 ,      16, hcc8    ,    17, dih8
 h,  17, hc9 ,      16, hcc9    ,    18, dih9
 c,  17, cc10,      16, ccc10   ,    18, dih10
 c,  18, cc11,      16, ccc11   ,    17, dih11
 h,  22, hc12,      18, hcc12   ,    16, dih12
 h,  21, hc13,      17, hcc13   ,    16, dih13
 c,  21, cc14,      17, ccc14   ,    16, dih14
 h,  25, hc15,      21, hcc15   ,    17, dih15

}

basis=6-31G*

{rhf;wf,96,1,0}

put,molden,rhf.s0.rot1814.optg.molden

{multi
noextra;
maxiter,40;
closed,20,19;occ,27,26
wf,96,1,0;state,1}

put,molden,rot1814.optg.mcscf.molden

{optg
inactive dih5;}

put,molden,rot1814.optg.molden

rs2c

---

I run this optimization on the cineca supercoputer plx using the following script:
#!/bin/bash
#PBS -l select=1:ncpus=12:mpiprocs=12:mem=47GB
#PBS -l walltime=24:00:00
#PBS -q longpar
#PBS -A *****

export TMPDIR=$CINECA_SCRATCH
cd $PBS_O_WORKDIR
module load autoload molpro
molpro -n12 rot1814.sp.optg.inp

The optimization finished and gave me an energy of ENERGY=-569.15192930. The program wasn't able to run CASPT2 calculation so I took the optimized structure and I performed a single point calculation on another machine using 4 processors and the following input:
 ***,(C2)
 memory,550, m
 gprint,basis,orbitals,civector
 file,2,rot1814.optg.sp.wfn,new
 punch,rot1814.optg.sp.pun,new

 geomtyp=xyz

 Geometry={
    24
  MULTI000/6-31G*  ENERGY=-569.15192930
  N         -0.5325246258       -0.4032695280       -1.4214415833
  N          0.5325246258        0.4032695280       -1.4214415833
  C         -1.5570952519       -0.1176059733       -0.5751681918
  C         -1.5875016866        0.9782914822        0.3240902310
  C         -2.6828117999       -0.9753265702       -0.6372874957
  H         -2.6542458744       -1.8035492359       -1.3200190152
  H         -0.7475337514        1.6417051215        0.3892917572
  C         -2.7055206902        1.1877869496        1.1168675931
  C         -3.7858422447       -0.7425057332        0.1659015099
  H         -4.6345043297       -1.3999893704        0.1103274814
  H         -2.7223557940        2.0205059709        1.7966704857
  C         -3.7995693614        0.3358445641        1.0417221045
  H         -4.6589748201        0.5118515444        1.6631715504
  C          1.5570952519        0.1176059733       -0.5751681918
  C          1.5875016866       -0.9782914822        0.3240902310
  C          2.6828117999        0.9753265702       -0.6372874957
  H          2.6542458744        1.8035492359       -1.3200190152
  H          0.7475337514       -1.6417051215        0.3892917572
  C          2.7055206902       -1.1877869496        1.1168675931
  C          3.7858422447        0.7425057332        0.1659015099
  H          4.6345043297        1.3999893704        0.1103274814
  H          2.7223557940       -2.0205059709        1.7966704857
  C          3.7995693614       -0.3358445641        1.0417221045
  H          4.6589748201       -0.5118515444        1.6631715504
 }

 basis=6-31G*

 {rhf;wf,96,1,0}

 put,molden,rhf.rot1814.optg.sp.molden

 {multi
 noextra;
 maxiter,40;
 closed,20,19;occ,27,26
 wf,96,1,0;state,1}

 put,molden,rot1814.optg.sp.mcscf.molden

 rs2c

 ---

I expected the same convergence value at the end of the mcscf cycles as I got in other previous calculation. But this time was different. After the mcscf cycle I obtained an energy value of -569.15359016. Why I got this difference? The only parameters that changed was the number of the processors and the memory required. Do you have  any hint to avoid these instabilities? 
I also tried to redo a new optimization starting from the geometry obtained from the first and I god a third new value. What is the value that I need to trust? Can you give me any hint to avoid these instabilities?
Thank you very much for your attention.

Valentina Cantatore
PhD student
Università di Pisa


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