Multiconfiguration pair-density functional theory investigation of the electronic spectrum of MnO4 -

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Abstract

The electronic spectrum of permanganate ions contains various highly multiconfigurational ligand-to-metal charge transfer states and is notorious for being one of the most challenging systems to be treated by quantum-chemical methods. Here we studied the lowest nine vertical excitation energies using restricted active space second-order perturbation theory (RASPT2) and multiconfiguration pair-density functional theory (MC-PDFT) to test and compare these two theories in computing such a challenging spectrum. The results are compared to literature data, including time-dependent density functional theory, completely renormalized equation-of-motion couple-cluster theory with single and double excitations, symmetry-adapted-cluster configuration interaction, and experimental spectra in the gas phase and solution. Our results show that MC-PDFT accurately predicts the spectrum at a significantly reduced cost as compared to RASPT2.

Original languageEnglish (US)
Article number124305
JournalJournal of Chemical Physics
Volume148
Issue number12
DOIs
StatePublished - Mar 28 2018

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electronic spectra
Density functional theory
density functional theory
Excitation energy
configuration interaction
excitation
Equations of motion
Charge transfer
equations of motion
perturbation theory
Gases
Metals
charge transfer
Ions
vapor phases
Ligands
costs
ligands
symmetry
metals

PubMed: MeSH publication types

  • Journal Article

Cite this

Multiconfiguration pair-density functional theory investigation of the electronic spectrum of MnO4 - . / Sharma, Prachi; Truhlar, Donald G.; Gagliardi, Laura.

In: Journal of Chemical Physics, Vol. 148, No. 12, 124305, 28.03.2018.

Research output: Contribution to journalArticle

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