Valence ππ∗ Excitations in Benzene Studied by Multiconfiguration Pair-Density Functional Theory

Prachi Sharma, Varinia Bernales, Donald G Truhlar, Laura Gagliardi

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Abstract

We explore the valence singlet and triplet ππ∗ excitations of benzene with complete active pace self-consistent field (CASSCF) theory, complete active space perturbation theory (CASPT2), and multiconfiguration pair-density functional theory (MC-PDFT) for four different choices of active space. We propose a new way to quantify the covalent and ionic character of the electronic states in terms of the components of the total electronic energy. We also explore the effect of scaling the exchange and correlation components of the on-top density functional used in MC-PDFT; we observe that increasing the exchange contribution improves the MC-PDFT excitation energies for benzene.

Original languageEnglish (US)
Pages (from-to)75-81
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume10
Issue number1
DOIs
StatePublished - Jan 3 2019

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Benzene
Density functional theory
benzene
density functional theory
valence
excitation
Excitation energy
Electronic states
electronics
atomic energy levels
self consistent fields
perturbation theory
scaling
energy

PubMed: MeSH publication types

  • Journal Article

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Valence ππ∗ Excitations in Benzene Studied by Multiconfiguration Pair-Density Functional Theory. / Sharma, Prachi; Bernales, Varinia; Truhlar, Donald G; Gagliardi, Laura.

In: Journal of Physical Chemistry Letters, Vol. 10, No. 1, 03.01.2019, p. 75-81.

Research output: Contribution to journalArticle

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