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
CountryGreece
CityPsalidi, Kos
Period3/10/108/10/10

Fingerprint

density functional theory
projection
functionals
occupation
broken symmetry
orbitals
electrons

Keywords

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

Cite this

Nakano, M., Minami, T., Fukui, H., Yoneda, K., Shigeta, Y., Kishi, R., ... Botek, E. (2015). Approximate spin projected spin-unrestricted density functional theory method: Application to diradical character dependences of second hyperpolarizabilities. In T. E. Simos, T. E. Simos, G. Maroulis, T. E. Simos, & T. E. Simos (Eds.), Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010 (pp. 30-34). [4906627] (AIP Conference Proceedings; Vol. 1642). American institute of physics. https://doi.org/10.1063/1.4906627
Nakano, Masayoshi ; Minami, Takuya ; Fukui, Hitoshi ; Yoneda, Kyohei ; Shigeta, Yasuteru ; Kishi, Ryohei ; Champagne, Benoît ; Botek, Edith. / Approximate spin projected spin-unrestricted density functional theory method : Application to diradical character dependences of second hyperpolarizabilities. Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010. editor / Theodore E. Simos ; Theodore E. Simos ; George Maroulis ; Theodore E. Simos ; Theodore E. Simos. American institute of physics, 2015. pp. 30-34 (AIP Conference Proceedings).
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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.",
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author = "Masayoshi Nakano and Takuya Minami and Hitoshi Fukui and Kyohei Yoneda and Yasuteru Shigeta and Ryohei Kishi and Beno{\^i}t Champagne and Edith Botek",
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Nakano, M, Minami, T, Fukui, H, Yoneda, K, Shigeta, Y, Kishi, R, Champagne, B & Botek, E 2015, Approximate spin projected spin-unrestricted density functional theory method: Application to diradical character dependences of second hyperpolarizabilities. in TE Simos, TE Simos, G Maroulis, TE Simos & TE Simos (eds), Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010., 4906627, AIP Conference Proceedings, vol. 1642, American institute of physics, pp. 30-34, International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010, Psalidi, Kos, Greece, 3/10/10. https://doi.org/10.1063/1.4906627

Approximate spin projected spin-unrestricted density functional theory method : Application to diradical character dependences of second hyperpolarizabilities. / Nakano, Masayoshi; Minami, Takuya; Fukui, Hitoshi; Yoneda, Kyohei; Shigeta, Yasuteru; Kishi, Ryohei; Champagne, Benoît; Botek, Edith.

Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010. ed. / Theodore E. Simos; Theodore E. Simos; George Maroulis; Theodore E. Simos; Theodore E. Simos. American institute of physics, 2015. p. 30-34 4906627 (AIP Conference Proceedings; Vol. 1642).

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

TY - GEN

T1 - Approximate spin projected spin-unrestricted density functional theory method

T2 - Application to diradical character dependences of second hyperpolarizabilities

AU - Nakano, Masayoshi

AU - Minami, Takuya

AU - Fukui, Hitoshi

AU - Yoneda, Kyohei

AU - Shigeta, Yasuteru

AU - Kishi, Ryohei

AU - Champagne, Benoît

AU - Botek, Edith

PY - 2015/1/1

Y1 - 2015/1/1

N2 - 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.

AB - 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.

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KW - diradical

KW - open-shell

KW - second hyperpolarizability

KW - spin projection

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DO - 10.1063/1.4906627

M3 - Conference contribution

T3 - AIP Conference Proceedings

SP - 30

EP - 34

BT - Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010

A2 - Simos, Theodore E.

A2 - Simos, Theodore E.

A2 - Maroulis, George

A2 - Simos, Theodore E.

A2 - Simos, Theodore E.

PB - American institute of physics

ER -

Nakano M, Minami T, Fukui H, Yoneda K, Shigeta Y, Kishi R et al. Approximate spin projected spin-unrestricted density functional theory method: Application to diradical character dependences of second hyperpolarizabilities. In Simos TE, Simos TE, Maroulis G, Simos TE, Simos TE, editors, Proceedings of the International Conference of Computational Methods in Sciences and Engineering 2010, ICCMSE 2010. American institute of physics. 2015. p. 30-34. 4906627. (AIP Conference Proceedings). https://doi.org/10.1063/1.4906627