Origin of the enhancement of the second hyperpolarizabilities in open-shell singlet transition-metal systems with metal-metal multiple bonds

H. Fukui, M. Nakano, Y. Shigeta, B. Champagne

Résultats de recherche: Contribution à un journal/une revueArticle

19 Downloads (Pure)

Résumé

Using the spin-unrestricted coupled-cluster method, we explore the origin of the second hyperpolarizabilities (γ) of singlet dichromium(II) and dimolybdenum(II) model systems with various bond lengths as a function of the diradical characters of the dσ, dπ, and dδ orbitals. Both systems exhibit enhanced γ values in the intermediate diradical character region, but by using a partitioning scheme, the dσ electrons are shown to play the essential role in contrast with the π-electrons of conventional organic π-conjugated systems. Then, in the equilibrium bond length region, the γ values are still governed by dσ electrons in the dichromium(II) system, although by dδ/dπ electrons in the dimolybdenum(II) system.
langue originaleAnglais
Pages (de - à)2063-2066
Nombre de pages4
journalJournal of Physical Chemistry Letters
Volume2
Numéro de publication16
Les DOIs
étatPublié - 18 août 2011

Empreinte digitale

Transition metals
Metals
transition metals
Electrons
augmentation
Bond length
metals
electrons
orbitals

Citer ceci

@article{fc6849b207984715a2231a2e723910cc,
title = "Origin of the enhancement of the second hyperpolarizabilities in open-shell singlet transition-metal systems with metal-metal multiple bonds",
abstract = "Using the spin-unrestricted coupled-cluster method, we explore the origin of the second hyperpolarizabilities (γ) of singlet dichromium(II) and dimolybdenum(II) model systems with various bond lengths as a function of the diradical characters of the dσ, dπ, and dδ orbitals. Both systems exhibit enhanced γ values in the intermediate diradical character region, but by using a partitioning scheme, the dσ electrons are shown to play the essential role in contrast with the π-electrons of conventional organic π-conjugated systems. Then, in the equilibrium bond length region, the γ values are still governed by dσ electrons in the dichromium(II) system, although by dδ/dπ electrons in the dimolybdenum(II) system.",
author = "H. Fukui and M. Nakano and Y. Shigeta and B. Champagne",
year = "2011",
month = "8",
day = "18",
doi = "10.1021/jz2007897",
language = "English",
volume = "2",
pages = "2063--2066",
journal = "The Journal of Physical Chemistry Letters",
issn = "0366-7022",
publisher = "Chemical Society of Japan",
number = "16",

}

Origin of the enhancement of the second hyperpolarizabilities in open-shell singlet transition-metal systems with metal-metal multiple bonds. / Fukui, H.; Nakano, M.; Shigeta, Y.; Champagne, B.

Dans: Journal of Physical Chemistry Letters, Vol 2, Numéro 16, 18.08.2011, p. 2063-2066.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Origin of the enhancement of the second hyperpolarizabilities in open-shell singlet transition-metal systems with metal-metal multiple bonds

AU - Fukui, H.

AU - Nakano, M.

AU - Shigeta, Y.

AU - Champagne, B.

PY - 2011/8/18

Y1 - 2011/8/18

N2 - Using the spin-unrestricted coupled-cluster method, we explore the origin of the second hyperpolarizabilities (γ) of singlet dichromium(II) and dimolybdenum(II) model systems with various bond lengths as a function of the diradical characters of the dσ, dπ, and dδ orbitals. Both systems exhibit enhanced γ values in the intermediate diradical character region, but by using a partitioning scheme, the dσ electrons are shown to play the essential role in contrast with the π-electrons of conventional organic π-conjugated systems. Then, in the equilibrium bond length region, the γ values are still governed by dσ electrons in the dichromium(II) system, although by dδ/dπ electrons in the dimolybdenum(II) system.

AB - Using the spin-unrestricted coupled-cluster method, we explore the origin of the second hyperpolarizabilities (γ) of singlet dichromium(II) and dimolybdenum(II) model systems with various bond lengths as a function of the diradical characters of the dσ, dπ, and dδ orbitals. Both systems exhibit enhanced γ values in the intermediate diradical character region, but by using a partitioning scheme, the dσ electrons are shown to play the essential role in contrast with the π-electrons of conventional organic π-conjugated systems. Then, in the equilibrium bond length region, the γ values are still governed by dσ electrons in the dichromium(II) system, although by dδ/dπ electrons in the dimolybdenum(II) system.

UR - http://www.scopus.com/inward/record.url?scp=80051927831&partnerID=8YFLogxK

U2 - 10.1021/jz2007897

DO - 10.1021/jz2007897

M3 - Article

AN - SCOPUS:80051927831

VL - 2

SP - 2063

EP - 2066

JO - The Journal of Physical Chemistry Letters

JF - The Journal of Physical Chemistry Letters

SN - 0366-7022

IS - 16

ER -