transition dipole moment of the same exact state!

Ahmad Almasri Alwan

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Apr 26, 2021, 8:34:11 AM4/26/21

to molpro-user

Dear MOLPRO users and experts

I´m trying to calculate the transition dipole moment between the ground state and an excited state considering a range of internuclear distances.

The main issue here is that for some internucleare distances, I´m getting the transition dipople moment between the ground state and its self!

How do I fix that?

Thanks in advance for your feecback

Here are the output and the input

The output part where it shows the TDMs between the ground state and its self:

**********************************************************************************************************************************

1PROGRAM * CI (Multireference internally contracted CI) Authors: H.-J. Werner, P.J. Knowles, 1987

Transition moment calculation

=============================

Ket wavefunction restored from record 7020.2 to file 8

Bra wavefunction restored from record 6030.3 to file 7

!MRCI overlap <1.1||1.1> 0.027196084097

!MRCI expec <1.1|DMZ|1.1> -0.392185978322 au = -0.996772038784 Debye

**********************************************************************************************************************************

The input file

***,SiN

Memory,520000000;

Gprint,basis;

Gprint,orbital;

geometry={ANGSTROM;

Si;

N,1,1.5850;

}

basis={

Si=aug-cc-PV6Z

N=aug-cc-PV6Z

}

{hf;

wf,21,1,1;

orbprint,1500;

}

{multi;

orbital,IGNORE_ERROR=1

occ,11,4,4,0;

closed,4,1,1,0;

wf,21,1,1;state,5;

wf,21,2,1;state,6;

wf,21,3,1;state,6;

wf,21,4,1;state,3;

}

!**************** CI ***************

r0 = 1.70

step = 0.02

do i = 1,1

r = r0 + (i-1)*step

dist(i) = r

geometry = {ANGSTROM;

Si;

N,1,r;

}

!******** Multi *********

multi;

orbital,IGNORE_ERROR=1

occ,11,4,4,0;

closed,4,1,1,0;

wf,21,1,1;state,5;

wf,21,2,1;state,6;

wf,21,3,1;state,6;

wf,21,4,1;state,3;

! we calculated the LZ, I didn't mentioned it here to make the post short

{ci,NOCHECK;

maxiter,60;

pspace,0.8;

occ,11,4,4,0;

closed,4,1,1,0;

core,4,1,1,0;

wf,21,1,1;state,1,2;option,nstati=1;save,6030.3}

{ci,NOCHECK;

maxiter,60;

orbital,IGNORE_ERROR=1

pspace,0.8;

occ,11,4,4,0;

closed,4,1,1,0;

core,4,1,1,0;

wf,21,1,1;state,1,1;option,nstati=1;save,7020.2}

{ci,NOCHECK;

trans,6030.3,7020.2,DMX,DMY,DMZ}

DSigma_DSigmax(i)=TRDMX(1)

DSigma_DSigmay(i)=TRDMY(1)

DSigma_DSigmaz(i)=TRDMZ(1)

table,dist,D_Lz_1_2,D_Lz_1_1,DSigma_DSigmax,DSigma_DSigmay,DSigma_DSigmaz

DIGITS,,8

enddo

put,molden,SiN.molden

Hans-Joachim Werner

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Apr 26, 2021, 11:03:52 AM4/26/21

to Ahmad Almasri Alwan, molpro-user

use in ci state,2 instead of state,1,1 or state,1,2; or use the project method, see manual
---
Prof. Dr. Hans-Joachim Werner
Institut für Theoretische Chemie
Universität Stuttgart
Pfaffenwaldring 55
70569 Stuttgart, Germany
e-mail: wer...@theochem.uni-stuttgart.de

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Ahmad Almasri Alwan

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Apr 27, 2021, 5:47:49 AM4/27/21

to molpro-user

Thank you so much for the correction, I tried the ci state,2

It looks better now.

it gives me the output below

However, <1.1|DMZ|2.1> can be only found in this section of the output, not anywhere else

The program still gives us the <1.1|DMZ|1.1> value in the table at the end as the answer

Thank you

Best regards

Ahmad

**********************************************************************************************************************************

1PROGRAM * CI (Multireference internally contracted CI) Authors: H.-J. Werner, P.J. Knowles, 1987

Transition moment calculation

=============================

Ket wavefunction restored from record 7020.2 to file 8

Bra wavefunction restored from record 6030.3 to file 7

!MRCI overlap <1.1||1.1> 0.018171945724

!MRCI expec <1.1|DMZ|1.1> -0.383190197022 au = -0.973908540948 Debye

!MRCI overlap <1.1||2.1> 0.999784802450

!MRCI trans <1.1|DMZ|2.1> -1.041003762632 au = -2.645794343031 Debye

**********************************************************************************************************************************

DATASETS * FILE NREC LENGTH (MB) RECORD NAMES

1 21 91.76 500 610 700 900 701 950 970 1000 129 960

VAR BASINP GEOM SYMINP GEOM ZMAT AOBASIS BASIS P2S ABASIS

1100 1400 1410 1200 1210 1080 1600 1650 1700 1380

S T V H0 H01 AOSYM SMH MOLCAS OPER JKOP

1700(1)

OPER

2 6 653.85 700 1000 2100 1 701 7020

GEOM BASIS RHF MCSCF GEOM MRCI

3 4 302.48 700 1000 701 6030

GEOM BASIS GEOM MRCI

PROGRAMS * TOTAL CI CI CI MULTI INT MULTI HF INT

CPU TIMES * 5746.85 25.28 2912.03 1641.77 252.48 49.31 811.74 5.09 49.06

REAL TIME * 5959.80 SEC

DISK USED * 8.58 GB

SF USED * 10.52 GB

GA USED * 0.00 MB (max) 0.00 MB (current)

**********************************************************************************************************************************

SETTING DSIGMA_DSIGMAX(1) = 0.00000000 AU

SETTING DSIGMA_DSIGMAY(1) = 0.00000000 AU

SETTING DSIGMA_DSIGMAZ(1) = -0.38319020 AU

DIST D_LZ_1_2 D_LZ_1_1 DSIGMA_DSIGMAX DSIGMA_DSIGMAY DSIGMA_DSIGMAZ

1.7 0.00000033 0.00000047 0.0 0.0 -0.38319020

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