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

Jan Franz jan.franz at chem.gu.se
Fri Jul 31 10:29:14 BST 2009

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

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