Excited state second hyperpolarizability

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pandey28
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Excited state second hyperpolarizability

Post by pandey28 » 03 Feb 2020, 01:31

Hi,

I want to calculate the cubic response (second hyperpolarizability) of CO2, but on an excited state instead of the ground state. It seems that Dalton does its calculations with respect to a reference state, which is usually the ground state. Is there a way I can set an excited state as the reference state, to get the second hyperpolarizability on the excited state?

Thanks

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magnus
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Re: Excited state second hyperpolarizability

Post by magnus » 04 Feb 2020, 22:42

You can get excited-state polarizabilities from the double residue of the cubic response function but not hyperpolarizabilities.

kennethruud
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Re: Excited state second hyperpolarizability

Post by kennethruud » 05 Feb 2020, 06:40

CO2 is small enough that you may consider also doing an MCSCF calculation, selecting the excited state of interest as the reference state. You can then get the second hyperpolarizability by performing a MCSCF cubic response calculation.

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magnus
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Re: Excited state second hyperpolarizability

Post by magnus » 05 Feb 2020, 09:38

Yes, of course. Didn't consider MCSCF :oops:

pandey28
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Re: Excited state second hyperpolarizability

Post by pandey28 » 09 Feb 2020, 21:39

@kennethruud: How exactly do I "select the excited state of interest as the reference"?

kennethruud
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Re: Excited state second hyperpolarizability

Post by kennethruud » 09 Feb 2020, 22:19

In the
**WAVE FUNCTION
....
*CONFIGURATION
.SYMMETRY
2 <- Symmetry of the excited state
.STATE
2 <- Second state (i.e. first excited state) of symmetry 2.

See Dalton 2018 manual pages 294-299.

Kenneth

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