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

[Jan Franz]

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