Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes

Taishi Yamada; Shota Takamuku; Hiroshi Matsui; Benoît Champagne; Masayoshi Nakano

doi:10.1016/j.cplett.2014.05.064

Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes

Taishi Yamada, Shota Takamuku, Hiroshi Matsui, Benoît Champagne, Masayoshi Nakano

Unit of theoretical and structural physico-chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

We investigate the axial ligand effects on the diradical character (y) dependences of the second hyperpolarizabilities (γ) of transition-metal dinuclear complexes, Mo(I)₂(CO)₂, with different bond lengths (R) using the spin-unrestricted coupled-cluster method. Mo(I) ₂(CO)₂ exhibits intrinsic y-γ correlation and dominant dσ-electron contribution to the maximum γ (γ_max), which are also observed in the bare dinuclear analogs. The axial-ligand coordination to Mo(I)₂ is found to cause the increase of the diradical character of the dσ orbital, the emergence of large negative γ for small R, and an enhancement of |γ _max| by a factor of ∼30 as compared to the bare analogs.

Original language	English
Pages (from-to)	68-73
Number of pages	6
Journal	Chemical Physics Letters
Volume	608
DOIs	https://doi.org/10.1016/j.cplett.2014.05.064
Publication status	Published - 2014

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10.1016/j.cplett.2014.05.064

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title = "Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes",

abstract = "We investigate the axial ligand effects on the diradical character (y) dependences of the second hyperpolarizabilities (γ) of transition-metal dinuclear complexes, Mo(I)2(CO)2, with different bond lengths (R) using the spin-unrestricted coupled-cluster method. Mo(I) 2(CO)2 exhibits intrinsic y-γ correlation and dominant dσ-electron contribution to the maximum γ (γmax), which are also observed in the bare dinuclear analogs. The axial-ligand coordination to Mo(I)2 is found to cause the increase of the diradical character of the dσ orbital, the emergence of large negative γ for small R, and an enhancement of |γ max| by a factor of ∼30 as compared to the bare analogs.",

author = "Taishi Yamada and Shota Takamuku and Hiroshi Matsui and Beno{\^i}t Champagne and Masayoshi Nakano",

year = "2014",

doi = "10.1016/j.cplett.2014.05.064",

language = "English",

volume = "608",

pages = "68--73",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

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TY - JOUR

T1 - Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes

AU - Yamada, Taishi

AU - Takamuku, Shota

AU - Matsui, Hiroshi

AU - Champagne, Benoît

AU - Nakano, Masayoshi

PY - 2014

Y1 - 2014

N2 - We investigate the axial ligand effects on the diradical character (y) dependences of the second hyperpolarizabilities (γ) of transition-metal dinuclear complexes, Mo(I)2(CO)2, with different bond lengths (R) using the spin-unrestricted coupled-cluster method. Mo(I) 2(CO)2 exhibits intrinsic y-γ correlation and dominant dσ-electron contribution to the maximum γ (γmax), which are also observed in the bare dinuclear analogs. The axial-ligand coordination to Mo(I)2 is found to cause the increase of the diradical character of the dσ orbital, the emergence of large negative γ for small R, and an enhancement of |γ max| by a factor of ∼30 as compared to the bare analogs.

AB - We investigate the axial ligand effects on the diradical character (y) dependences of the second hyperpolarizabilities (γ) of transition-metal dinuclear complexes, Mo(I)2(CO)2, with different bond lengths (R) using the spin-unrestricted coupled-cluster method. Mo(I) 2(CO)2 exhibits intrinsic y-γ correlation and dominant dσ-electron contribution to the maximum γ (γmax), which are also observed in the bare dinuclear analogs. The axial-ligand coordination to Mo(I)2 is found to cause the increase of the diradical character of the dσ orbital, the emergence of large negative γ for small R, and an enhancement of |γ max| by a factor of ∼30 as compared to the bare analogs.

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U2 - 10.1016/j.cplett.2014.05.064

DO - 10.1016/j.cplett.2014.05.064

M3 - Article

AN - SCOPUS:84902653799

SN - 0009-2614

VL - 608

SP - 68

EP - 73

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes

Abstract

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Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes

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Projects

PAI n°P7/05 - FS2: Functional Supramolecular Systems (FS2)

TINTIN - ARC 09/14-23: Molecular TINkertoys for OpToelectronics and SpINtronics - TINTIN

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High Performance Computing Technology Platform

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