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Created September 17, 2020 05:17
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TDM Calculations - ORCA

Transition Dipole moment calculation using ORCA:

Current latest version, namely version 3.6(dev) of Multiwfn is able to calculate transition dipole moment between excited states based on ORCA output.

First, conduct a CIS or TDA-DFT calculation using keywords like below, assume that file name is test.inp ! PBE0 def2-SVP nopop pal4 %tddft nroots 4 tprint 1E-8 end

Then use such as "orca_2mkl test -molden" command to convert test.gbw to test.molden.input

Finally, boot up Multiwfn and input test.molden.input // The .molden input file 18 // Electronic excitation analyses 5 // Calculate transition electric dipole moments between all excited states test.out // The ORCA output file 1 // Output transition dipole moments to screen Now you will find below result on screen.

Ground state dipole moment in X,Y,Z: -0.271701 -0.314645 0.344277 a,u,

Transition dipole moment between excited states (a.u.): i j X Y Z Diff.(eV) Oscil.str 1 1 -1.7862676 -0.2640772 0.2405912 0.00000 0.00000 1 2 0.1976941 0.0854227 0.0346682 0.70800 0.00083 1 3 2.1779748 -0.1165127 0.1223195 1.38100 0.16146 1 4 -0.4226960 0.0657206 -0.0047136 1.73500 0.00778 2 2 -2.6132918 -0.1285522 0.0996265 0.00000 0.00000 2 3 0.0625351 0.3407469 -0.0481496 0.67300 0.00202 2 4 0.2904364 -0.1027734 -0.2020122 1.02700 0.00341 3 3 -2.9400691 -0.2538387 0.1676538 0.00000 0.00000 3 4 0.4640359 0.0322024 -0.0096710 0.35400 0.00188 4 4 2.3204590 1.0665381 -0.2011480 0.00000 0.00000

The i and j are excited state indices, the line such as i=2 and j=2 corresponds to electronic dipole moment of excited state 2.

This feature of Multiwfn should work perfectly for CIS and TDA-DFT. However, for the TDHF or TDDFT, the result may be not always reliable, since in this case, current version of ORCA does not output excitation configuration coefficients and de-excitation configuration coefficients separately, which are needed for strictly evaluating transition dipole moments.

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