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@JonathonMisiewicz JonathonMisiewicz commented Jan 11, 2023

Description

My previous PRs fixed the bugs making UKS TDDFT and stability analysis incorrect, so let's enable them.

User API & Changelog headlines

  • Stability analysis is now supported for unrestricted GGAs.
  • TDDFT is now supported for unrestricted GGAs.

Dev notes & details

  • The prohibition against VV10 is not added to this PR, but its enforcement is. The old code would have given incorrect results.

Checklist

  • Tests mostly pass. test_tdscf_excitations.py has this PR covered. The one complication is that we're failing the TDA and RPA tests for CH2 with HCTH93. My investigations lead me to suspect the fault is bad reference data, probably involving pruned integration grids. @bgpeyton has confirmed pruning as the issue and volunteered to re-generate proper data.

Status

  • Ready for review
  • Ready for merge

@JonathonMisiewicz JonathonMisiewicz added feature Extends an existing Psi feature or develops a new one. dft For issues specific to DFT and their many functionals. labels Jan 11, 2023
@susilehtola
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I would consider not making VV10 throw an error, since it has negligible effects on the electron density. Najibi and Goerigk write in doi:10.1021/acs.jctc.8b00842

While in a strictest sense, energy calculations with vdW-DFAs should be carried out fully self-consistently, we demonstrate conclusively for a total of 11 methods that such a strategy only increases the computational time effort without having any significant effect on energetic properties, electron densities, or orbital-energy differences.

The recent analytical frequencies study by Feng, Liang and Head-Gordon in arXiv:2208.14639 states

The contribution of VV10 to simulating harmonic frequencies is shown to be small for small molecules but important for systems where weak interactions are important, such as water clusters.

That manuscript does have analytical second derivatives, so I guess one could extend it to TDDFT as well?

@JonathonMisiewicz
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Psi has a mechanism to make VV10 a post-iteration correction. How about allowing stability analysis / TDDFT if VV10 is post-iterative, and raising an error otherwise, directing users to make VV10 post-iterative?

@hokru
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hokru commented Jan 12, 2023

I think it is a bit of an open questions how to exactly incorporate a VV10 dispersion treatment for excited states.

@JonathonMisiewicz JonathonMisiewicz added this to the Psi4 1.8 milestone Jan 23, 2023
@JonathonMisiewicz JonathonMisiewicz marked this pull request as draft January 26, 2023 15:23
@JonathonMisiewicz JonathonMisiewicz marked this pull request as draft January 26, 2023 15:23
@JonathonMisiewicz
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JonathonMisiewicz commented Jan 26, 2023

Converted this PR to a draft. I do no support merging this PR while a LibXC bug is under investigation. (Hat tip to the LibXC team for that investigation.)

@JonathonMisiewicz JonathonMisiewicz mentioned this pull request Jan 27, 2023
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@JonathonMisiewicz JonathonMisiewicz marked this pull request as ready for review February 10, 2023 03:05
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hooray!

# In Psi's sign convention, the "L" gauge needs a + sign, and the "V" gauge a -
# sign. Adjust for your case.
# In PySCF's sign convention, the velocity gauge electric and the magnetic dipole
# both have flipped sign.
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very good to know

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5 participants