Theoretical study on the spin state and open-shell character dependences of the second hyperpolarizability in hydrogen chain models

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Abstract

Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.

Original languageEnglish
Article number042515
JournalPhysical Review A - Atomic, Molecular, and Optical Physics
Volume94
Issue number4
DOIs
Publication statusPublished - 28 Oct 2016

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hydrogen
configuration interaction
tuning
ground state
approximation
excitation

Keywords

  • quantum chemistry
  • spin state
  • open-shell character
  • second hyperpolarisabillity

Cite this

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title = "Theoretical study on the spin state and open-shell character dependences of the second hyperpolarizability in hydrogen chain models",
abstract = "Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.",
keywords = "quantum chemistry, spin state, open-shell character, second hyperpolarisabillity",
author = "Hiroshi Matsui and Masayoshi Nakano and Beno{\^i}t Champagne",
year = "2016",
month = "10",
day = "28",
doi = "10.1103/PhysRevA.94.042515",
language = "English",
volume = "94",
journal = "Physical Review A - Atomic, Molecular, and Optical Physics",
issn = "1050-2947",
publisher = "American Physical Society",
number = "4",

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TY - JOUR

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AU - Matsui, Hiroshi

AU - Nakano, Masayoshi

AU - Champagne, Benoît

PY - 2016/10/28

Y1 - 2016/10/28

N2 - Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.

AB - Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.

KW - quantum chemistry

KW - spin state

KW - open-shell character

KW - second hyperpolarisabillity

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