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Alex Granovsky

gran@classic.chem.msu.su

Hello,

both X and Y are Nvir by Nocc matrices. Here Nvir is the number

of virtual orbitals and Nocc is the number of active (i.e. non-core)

occupied orbitals.

Kind regards,

Alex Granovsky

On Wed Aug 12 '15 2:38pm, Siddheshwar Chopra wrote

--------------------------------------------------

>Dear Sir,

>I have got the PUNCH file now from TDDFT output file.

>I was seeing the $TDVEC group. It was told that there are 2*NSTATE records in the PUNCH file. In my case, NSTATE=10. I found only 10 records. Some of the text is below:

> $TDVEC

> 111900 SAPS, 10 STATES

>STATE 1 ENERGY= -3138.3278180436

> 1.020442E-04 -5.608704E-05 2.396080E-05 -9.260984E-06 -6.636264E-05

> -2.286013E-05 9.396216E-06 4.878278E-06 -1.852484E-06 7.472925E-06

> -1.400424E-05 1.178049E-06 -1.364119E-05 -2.155512E-05 -5.376085E-07

> 2.311168E-05 2.947819E-05 -1.013776E-05 -1.373176E-05 5.238495E-05

> -1.988428E-05 -4.153096E-05 1.564358E-06 -2.853384E-05 2.364293E-05

> 8.782922E-06 1.376641E-05 7.302916E-07 -1.307850E-05 -2.573553E-05

> -2.404907E-05 -4.533857E-05 1.029407E-05 -5.705214E-06 1.335178E-05

> -1.349594E-05 1.777842E-05 2.651136E-05 -1.773483E-05 1.564974E-05

> 1.235830E-05 6.562604E-06 -5.306053E-06 1.476717E-05 3.225120E-06

>.....................

>..................... (in total 22380 lines for one state)

>Here as you said, "X" and "Y" are mentioned alternatively, X from 1st line onwards. I am unable to understand the size of the matrix (X or Y). Here "X" has 5 numbers. How to visualize this matrix?

>Also, NVIR and NOC were talked about. Are these the "number of alpha and beta orbitals"? In this case it is 206 then?

>Please elaborate about the construction of matrix. In case if PUNCH file is needed, I will send it privately, if only you permit.

>Regards,

>

>

>On Sat Oct 4 '14 7:16pm, Alex Granovsky wrote

>---------------------------------------------

>>Hi,

>>no, transition dipole moment matrix does not serve your purposes.

>>Kind regards,

>>Alex Granovsky

>>

>>

>>On Mon Sep 29 '14 11:49am, Siddheshwar Chopra wrote

>>---------------------------------------------------

>>>Dear Alex,

>>>Sorry for asking you again. There is a relation between transition density and transition dipole. So please pardon me if I ask:: Will extracting Transition dipole moment matrix serve the purpose of pointing out "spatial location of the transition from ground to excited state"? It is a NSTATE*NSTATE matrix as you told too.

>>>Kind Regards,

>>

>>

>>

>>

>>

>>>

>>>

>>>On Mon Sep 29 '14 11:13am, Siddheshwar Chopra wrote

>>>---------------------------------------------------

>>>>Dear Alex,

>>>>Thank you for the detailed explanation. I really need a TDDFT PUNCH file now to understand what you have suggested. I will get back once I extract this matrix.

>>>>In the meanwhile has anyone got a program for this extraction? It would be a great help.

>>>>Kind Regards,

>>>>On Sun Sep 28 '14 0:20am, Alex Granovsky wrote

>>>>----------------------------------------------

>>>>>Dear Siddheshwar,

>>>>>I'm sorry for delay with my answers.

>>>>>As to your questions:

>>>>>>>I would be really grateful if you could throw some light on the transition density matrix calculation. Is it possible to determine the matrix from TDDFT output file? IF yes then I would attach one file. Kindy let me know Sir.

>>>>>No, it is impossible to compute 1-P TDM (one-particle transition

>>>>>density matrix) based only on the information found in the output

>>>>>file.

>>>>>>>>Dear Pavlo Sir and Alex Sir,

>>>>>>>>Thank you so much for the useful information. Alex sir I am really happy to know that it is possible to find TDM from PUNCH file (from TDDFT calc.). I would request you to elaborate the process for the same. Right now I dont have any punch file with me. Can you explain with the help of any punch file? Once that is clear, I will look for the program.

>>>>>The required information that can be extracted from the PUNCH file

>>>>>is the content of the $VEC group and $TDVEC group. Each $VEC group

>>>>>contains current molecular orbitals. The $TDVEC group contains X

>>>>>and Y components of the TDDFT eigenvectors. For hybrid DFT, X

>>>>>component is written first, then Y component follows. These records

>>>>>are repeated for each root of TDDFT i.e. there are 2*NSTATE records

>>>>>in total. As to individual record, it contains NVIR*NOC elements,

>>>>>where NVIR is the number of virtual orbitals and NOC is the number

>>>>>of active occupied orbitals i.e. the number of occupied orbitals

>>>>>minus number of frozen core MOs. These numbers form matrices X

>>>>>and Y, with virtual orbital index running first, then occupied

>>>>>orbital index.

>>>>>Once you extracted X and Y matrices, the transition density matrix

>>>>>in MO basis is simply sum of X and Y blocks: Tmo = X+Y. If you need,

>>>>>you can convert it into MO basis set using the following equation:

>>>>>

Tao = S*V * Tmo * (S*V)-dagger

>>>>>where V are the matrix of MO coefficients and S is the matrix of

>>>>>overlap integrals. The latter can be printed out by running

>>>>>Firefly with exetyp=INT1

>>>>>>>>Also, Sir I found that transition dipole moment matrix in the TDDFT o/p file is of the size NSTATE X NSTATE. Can you explain how to analyse this? I find the x,y,z data corresponding to an i,j element.

>>>>>This is a matrix of transition dipoles between states Si and Sj.

>>>>>This information can be used, for instance, to compute

>>>>>two-photon absorbance (TPA)cross-sections using sum over states

>>>>>approach (SoS)

>>>>>> Does the magnitude of this dipole moment = sqrt(x^2+y^2+z^2)?

>>>>>Yes it is (note in the printout atomic units are used throughout).

>>>>>Kind regards,

>>>>>Alex Granovsky

Tue Aug 18 '15 6:01pm

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