[molpro-user] non-adiabatic coupling matrix - diagonal elements

Kirk Peterson kipeters at wsu.edu
Fri Jul 31 17:15:03 BST 2009


Dear Jan,

unfortunately Molpro is not able to compute diagonal Born-Oppenheimer  
corrections. At one point David Schwenke had coded this into Molpro as  
an add-on module and I had used this extensively in the past.  
Unfortunately this development was not kept current and it no longer  
works with any newer versions of the code. You could check with David  
to see if he has any updates to this (David.W.Schwenke at nasa.gov).   
Unless you need a multireference treatment, I would recommend to try  
either PSI3 (http://www.psicode.org) or CFOUR (http://www.cfour.de/),  
both of which are freely available and can calculate the DBOC up to  
the CCSD(T) level.

regards,

Kirk

On Jul 31, 2009, at 8:06 AM, jacek klos wrote:

> see here message from Kirk on similar topic: http://www.ccl.net/chemistry/resources/messages/2008/01/01.003-dir/index.html
> i dont know what is the status of the DBOC in the  2008.1 version
> best
> jacek
> On Jul 31, 2009, at 5:29 AM, Jan Franz wrote:
>
>> Dear all,
>> I would like to calculate diagonal matrix elements of non-adiabatic
>> coupling matrix
>> elements like:
>> <1.1| d/dR |1.1> and <2.1| d/dR |2.1>,
>> where the notation 2.1 means the second state in the first irrep.
>>
>> I am using the commands:
>> {DDR,DR,2140.2,2141.2,8111.2;STATE,1.1,1.1}
>>
>> and I am getting the output:
>>
>>
>> ...
>>
>> Construct non-adiabatic coupling elements by finite difference method
>>
>> Orbitals at R from                   2140.2 Type=NATURAL (state
>> averaged)
>> Orbitals at R+dR from                2141.2 Type=DIABATIC (state
>> averaged)
>>
>> CENTER 1 DISPLACED BY     0.000000    0.000000   -0.001268
>> CENTER 2 DISPLACED BY     0.000000    0.000000    0.008732
>>
>>
>> Delta R                          0.01000000
>>
>> Transition density (R|R+DR) from     8111.2 for states 1.1 - 1.1
>>
>>
>> **********************************************************************************************************************************
>> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>>
>> ...
>>
>>
>>
>> After reading the transition density matrix the program
>> does not print any numbers.
>>
>> It does for the non-diagonal matrix elements:
>> e.g. <1.1| d/dR |2.1>.
>>
>>
>> ...
>>
>> Construct non-adiabatic coupling elements by finite difference method
>>
>> Orbitals at R from                   2140.2 Type=NATURAL (state
>> averaged)
>> Orbitals at R+dR from                2141.2 Type=DIABATIC (state
>> averaged)
>>
>> CENTER 1 DISPLACED BY     0.000000    0.000000   -0.001268
>> CENTER 2 DISPLACED BY     0.000000    0.000000    0.008732
>>
>>
>> Delta R                          0.01000000
>>
>> Transition density (R|R+DR) from     8111.2 for states 2.1 - 1.1
>>
>> CI contribution:                -0.00187707
>> Overlap contribution:           -0.02549934
>> Orbital contribution:            0.02572541
>> !Total NACME:                   -0.00165100
>>
>>
>>
>> **********************************************************************************************************************************
>> DATASETS  * FILE   NREC   LENGTH (MB)   RECORD NAMES
>>
>> ...
>>
>>
>>
>>
>>
>>
>>
>> I would be very glad for any advice how to get the diagonal elements.
>>
>> I am using MOLPRO Version 2006.1.
>> My input file is given below.
>>
>>
>> Best regards,
>>
>> Jan
>>
>>
>>
>>
>>
>>
>>
>>
>> input file:
>>
>>
>>
>> memory,50,m
>> gprint orbital
>>
>> basis=AVTZ
>> geometry={
>> 	Li
>> 	H  Li  RLH
>> 	}
>>
>> RLH=1.7
>>
>>
>> RLHVEC=[1.7]
>>
>> DR=0.01;
>>
>>
>> {HF; WF,4,1,0}
>>
>> DO I=1,#RLHVEC
>>   RLH=RLHVEC(I)
>>
>> {   MULTI;
>>   CLOSED,0,0,0,0;
>>   OCC,4,2,2,1;
>>   WF,4,1,0;STATE,2;
>>   ORBITAL,2140.2;
>> }
>>
>>
>> {   CI;
>>   CORE,0,0,0,0;
>>   CLOSED,0,0,0,0;
>>   OCC,4,2,2,1;
>>   WF,4,1,0;STATE,2;
>>   SAVE,6011.2;
>>   NOEXC;
>> }
>>
>>
>>   {CI;TRANS,6011.2,6011.2;DM,8011.2}
>>
>>
>>   RLH=RLHVEC(I)+DR;
>>
>> {   MULTI;
>>   CLOSED,0,0,0,0;
>>   OCC,4,2,2,1;
>>   WF,4,1,0;STATE,2;
>>   START,2140.2;
>>   ORBITAL,2141.2;
>>   DIAB,2140.2;
>> }
>>
>>
>> {   CI;
>>   CORE,0,0,0,0;
>>   CLOSED,0,0,0,0;
>>   OCC,4,2,2,1;
>>   WF,4,1,0;STATE,2;
>>   SAVE,6111.2;
>>   NOEXC;
>> }
>>
>>
>>   {CI;TRANS,6011.2,6111.2;DM,8111.2}
>>
>>
>>
>>   RLH=RLHVEC(I)-DR;
>>
>> {   MULTI;
>>   CLOSED,0,0,0,0;
>>   OCC,4,2,2,1;
>>   WF,4,1,0;STATE,2;
>>   START,2140.2;
>>   ORBITAL,2142.2;
>>   DIAB,2140.2;
>> }
>>
>>
>> {   CI;
>>   CORE,0,0,0,0;
>>   CLOSED,0,0,0,0;
>>   OCC,4,2,2,1;
>>   WF,4,1,0;STATE,2;
>>   SAVE,6211.2;
>>   NOEXC;
>> }
>>
>>
>>   {CI;TRANS,6011.2,6211.2;DM,8211.2}
>>
>>
>>
>>
>>
>>   {DDR,DR,2140.2,2141.2,8111.2;STATE,1.1,1.1}
>>   {DDR,DR,2140.2,2141.2,8111.2;STATE,1.1,2.1}
>>   {DDR,DR,2140.2,2141.2,8111.2;STATE,2.1,2.1}
>>
>>   {DDR,-DR,2140.2,2141.2,8211.2;STATE,1.1,1.1}
>>   {DDR,-DR,2140.2,2141.2,8211.2;STATE,1.1,2.1}
>>   {DDR,-DR,2140.2,2141.2,8211.2;STATE,2.1,2.1}
>>
>>   {DDR,2*DR;ORBITAL,2140.2,2141.2,2142.2;DENSITY,
>> 8011.2,8111.2,8211.2;STATE,1.1,1.1}
>>   {DDR,2*DR;ORBITAL,2140.2,2141.2,2142.2;DENSITY,
>> 8011.2,8111.2,8211.2;STATE,1.1,2.1}
>>   {DDR,2*DR;ORBITAL,2140.2,2141.2,2142.2;DENSITY,
>> 8011.2,8111.2,8211.2;STATE,2.1,2.1}
>>
>>
>>
>>
>> ENDDO
>>
>>
>>
>>
>>
>>
>> -- 
>> Dr. Jan Franz
>> Institutionen för Kemi
>> Göteborg University
>> Kemivägen 10
>> 412 96 Göteborg
>> Sweden
>>
>> email: jan.franz at chem.gu.se
>> phone: +46 (0) 31 786 9032
>>
>> _______________________________________________
>> Molpro-user mailing list
>> Molpro-user at molpro.net
>> http://www.molpro.net/mailman/listinfo/molpro-user
>
> ---------------------------------------
> Jacek Klos, Ph. D.
> Department of Chemistry and Biochemistry
> University of Maryland
> College Park, MD 20742 USA
> tel: 1-301-405-1822
> fax: 1-301-314-9121
> http://www.researcherid.com/rid/A-6457-2008
> ----------------------------------------
>
>
>
> _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user




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