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lsimon

Member

Registered: 2023-03-04

Posts: 7

problem exporting .47 file for NBO containing the Fock Matrix

Trying to export a .47 file for its use with NBO, I noticed that the "Second Order Perturbation Theory Analysis of Fock Matrix in NBO Basis"  obtained after runing gennbo over this .47 file yields unrealistic results, with lots of overflows. Other parts of the NBO calculation seem to be OK, so I wonder if there is any change on the wavefunction that should be applied before exporting the .47 file (maybe some spherical or cartesian conversions) or if there is any problem with the format of the exported Fock matrix (maybe some units) that I will have to set in the NBO input file to prevent this problem.

Thanks in advanced:

Luis

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,631

Website

Re: problem exporting .47 file for NBO containing the Fock Matrix

I don't find this problem, at least for the .47 file converted from my test file "examples\N-phenylpyrrole.fch". NBO 7.0.7 runs normally based on the .47 file (containing Fock matrix) produced by Multiwfn, E2 analysis result is fully correct. Please provide more detailed information about the problem you encountered, such as basis set, chemical formula, software version, etc.

lsimon

Member

Registered: 2023-03-04

Posts: 7

Re: problem exporting .47 file for NBO containing the Fock Matrix

thanks a lot for the answer!

I am using NBO 5.0 (Is pretty old, but the one for which I have a license). The wavefunction that I am using comes from an ORCA 5.0  job, from which I used the gbw file to obtain a .molden.input file with orca_2mkl  program (with -molden option). I opened this file with Multiwfn 3.8 -the version without the graphic interface- installed on centos Linux, next I used the sequence of options 100-2-8-(name of the 47 file)-1.

I tried different basis set (def2TZVPPD and def2SVP) with similar outcome.

Maybe the problem is on my NBO very old version, which may have a different definition of the precision of the data. Keyword "FORMAT=PRECISE", that is used to specify the format of the data in the file .47, is not recognized in such an old NBO version

Some of the lines of the 2nd order perturbation theory section:

SECOND ORDER PERTURBATION THEORY ANALYSIS OF FOCK MATRIX IN NBO BASIS

     Threshold for printing:   0.50 kcal/mol
                                                          E(2)  E(j)-E(i) F(i,j)
      Donor NBO (i)              Acceptor NBO (j)       kcal/mol   a.u.    a.u.
===============================================================================

within unit  1
   1. BD ( 1) O 1- C12       52. RY*( 2) O 1           1368.32 1055.78   33.965
   1. BD ( 1) O 1- C12       55. RY*( 5) O 1          21237.89 6696.45  337.074
   1. BD ( 1) O 1- C12       56. RY*( 6) O 1          24462.6868992.73 1161.212
   1. BD ( 1) O 1- C12       57. RY*( 7) O 1           4105.20 1249.59   64.019
   1. BD ( 1) O 1- C12       60. RY*(10) O 1          ********11860.31 1045.866
   1. BD ( 1) O 1- C12       62. RY*(12) O 1          ******** 8637.36 1464.453

Best

Luis

lsimon

Member

Registered: 2023-03-04

Posts: 7

Re: problem exporting .47 file for NBO containing the Fock Matrix

sorry for not including this before!

I also repeated the calculation with the fch file in the /examples/ folder, and it works well.... so it seems that it is not a problem with NBO but probably with orca_2mkl program...

Thanks

Luis

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,631

Website

Re: problem exporting .47 file for NBO containing the Fock Matrix

I also tested using the .47 converted from ORCA .molden.input file with GENNBO 5.0, the E2 result is also reasonable.

lsimon

Member

Registered: 2023-03-04

Posts: 7

Re: problem exporting .47 file for NBO containing the Fock Matrix

Thanks for testing! I will make more tests and if I figure out the problem I will post the solution

Best

Luis

lsimon

Member

Registered: 2023-03-04

Posts: 7

Re: problem exporting .47 file for NBO containing the Fock Matrix

I have been experimenting with different files and observed that the problem is with ORCA calculations involving at least d functions (6-31G is ok but 6-31G* not), and not with wavefunctions generated by other programs (with Gaussian16 the result is OK). I also noticed that although ORCA uses 5 d functionals, Multiwfn uses 6. There is no problem with this transformation, at least the tests in the appendix 5 of the manual are passed, but could it be related with a problem generating the .47 file when it is read by NBO5?

Thanks

Luis

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,631

Website

Re: problem exporting .47 file for NBO containing the Fock Matrix

I just updated Multiwfn, d-type of spherical harmonic basis functions now can present in the inputted wavefunction file, and Fock matrix can be properly generated and written into .47 file.

However, spherical-harmonic basis functions with >d angular moment are still not supported yet by this function. Even though after setting "iloadasCart" in settings.ini to 1, the .47 file can be generated with Cartesian basis functions, the Fock matrix cannot be properly yielded and written into it, because in principle it is impossible to generate Fock matrix of 6d based on orbital energies and orbital coefficients originally produced by 5d quantum chemistry calculation.

Best,

Tian