Second Linear Response Theory and the Analytic Calculation of Excited-State Properties

Martín A. Mosquera, Leighton O. Jones, Gyeongwon Kang, Mark A. Ratner, George C. Schatz*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

We present a method based on second linear response time-dependent density functional theory (TDDFT) to calculate permanent and transition multipoles of excited states, which are required to compute excited-state absorption/emission spectra and multiphoton optical processes, among others. In previous work, we examined computations based on second linear response theory in which linear response TDDFT was employed twice. In contrast, the present methodology requires information from only a single linear response calculation to compute the excited-state properties. These are evaluated analytically through various algebraic operations involving electron repulsion integrals and excitation vectors. The present derivation focuses on full many-body wave functions instead of single orbitals, as in our previous approach. We test the proposed method by applying it to several diatomic and triatomic molecules. This shows that the computed excited-state dipoles are consistent with respect to reference equation-of-motion coupled-cluster calculations.

Original languageEnglish (US)
Pages (from-to)1093-1102
Number of pages10
JournalJournal of Physical Chemistry A
Volume125
Issue number4
DOIs
StatePublished - Feb 4 2021

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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