Approximate spin projected spin-unrestricted density functional theory method: Application to diradical character dependences of second hyperpolarizabilities

Masayoshi Nakano, Takuya Minami, Hitoshi Fukui, Kyohei Yoneda, Yasuteru Shigeta, Ryohei Kishi, Benoît Champagne, Edith Botek

Research output: Contribution in Book/Catalog/Report/Conference proceedingConference contribution

Abstract

We develop a novel method for the calculation and the analysis of the one-electron reduced densities in open-shell molecular systems using the natural orbitals and approximate spin projected occupation numbers obtained from broken symmetry (BS), i.e., spin-unrestricted (U), density functional theory (DFT) calculations. The performance of this approximate spin projection (ASP) scheme is examined for the diradical character dependence of the second hyperpolarizability (γ) using several exchange-correlation functionals, i.e., hybrid and long-range corrected UDFT schemes. It is found that the ASP-LC-UBLYP method with a range separating parameter μ = 0.47 reproduces semi-quantitatively the strongly-correlated [UCCSD(T)] result for p-quinodimethane, i.e., the γ variation as a function of the diradical character.

Original languageEnglish
Title of host publicationProceedings of the International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010
EditorsTheodore E. Simos, Theodore E. Simos, George Maroulis, Theodore E. Simos, Theodore E. Simos
PublisherAmerican institute of physics
Pages30-34
Number of pages5
ISBN (Electronic)9780735412828
DOIs
Publication statusPublished - 1 Jan 2015
EventInternational Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010 - Psalidi, Kos, Greece
Duration: 3 Oct 20108 Oct 2010

Publication series

NameAIP Conference Proceedings
Volume1642
ISSN (Print)0094-243X
ISSN (Electronic)1551-7616

Conference

ConferenceInternational Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010
Country/TerritoryGreece
CityPsalidi, Kos
Period3/10/108/10/10

Keywords

  • density functional theory
  • diradical
  • open-shell
  • second hyperpolarizability
  • spin projection
  • spin unrestricted

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