Theoretical investigation of the first hyperpolarizability redox-switching in a ruthenium complex

Yuexing Zhang; Frédéric Castet; Benoît Champagne

doi:10.1016/j.cplett.2013.04.071

Theoretical investigation of the first hyperpolarizability redox-switching in a ruthenium complex

Yuexing Zhang^*, Frédéric Castet, Benoît Champagne

^*Corresponding author for this work

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

15 Scopus citations

Abstract

The first hyperpolarizability (β) of [Ru^II-(NH ₃)₅(4-AcPhQ)]³⁺ and of its oxidized form [Ru^III-(NH₃)₅(4-AcPhQ)]⁴⁺, previously synthesized and characterized by Coe and co-workers by means of hyper-Rayleigh scattering measurements, has been calculated using time-dependent density functional theory and analyzed resorting to the summation-over-states scheme. Besides confirming a β contrast of at least one order of magnitude, calculations point out the key role of the metal-to-ligand charge transfer state, which is responsible for the larger β response of the reduced Ru(II) form. Results also evidence the small contribution to β of the higher-energy intra-ligand charge transfer excited states, as well as the small changes of the depolarization ratio upon oxidation.

Original language	English (US)
Pages (from-to)	42-46
Number of pages	5
Journal	Chemical Physics Letters
Volume	574
DOIs	https://doi.org/10.1016/j.cplett.2013.04.071
State	Published - Jun 14 2013
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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@article{a7b2b5c911c34f6fb87b2232afee7314,

title = "Theoretical investigation of the first hyperpolarizability redox-switching in a ruthenium complex",

abstract = "The first hyperpolarizability (β) of [RuII-(NH 3)5(4-AcPhQ)]3+ and of its oxidized form [RuIII-(NH3)5(4-AcPhQ)]4+, previously synthesized and characterized by Coe and co-workers by means of hyper-Rayleigh scattering measurements, has been calculated using time-dependent density functional theory and analyzed resorting to the summation-over-states scheme. Besides confirming a β contrast of at least one order of magnitude, calculations point out the key role of the metal-to-ligand charge transfer state, which is responsible for the larger β response of the reduced Ru(II) form. Results also evidence the small contribution to β of the higher-energy intra-ligand charge transfer excited states, as well as the small changes of the depolarization ratio upon oxidation.",

author = "Yuexing Zhang and Fr{\'e}d{\'e}ric Castet and Beno{\^i}t Champagne",

year = "2013",

month = jun,

day = "14",

doi = "10.1016/j.cplett.2013.04.071",

language = "English (US)",

volume = "574",

pages = "42--46",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier B.V.",

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TY - JOUR

T1 - Theoretical investigation of the first hyperpolarizability redox-switching in a ruthenium complex

AU - Zhang, Yuexing

AU - Castet, Frédéric

AU - Champagne, Benoît

PY - 2013/6/14

Y1 - 2013/6/14

N2 - The first hyperpolarizability (β) of [RuII-(NH 3)5(4-AcPhQ)]3+ and of its oxidized form [RuIII-(NH3)5(4-AcPhQ)]4+, previously synthesized and characterized by Coe and co-workers by means of hyper-Rayleigh scattering measurements, has been calculated using time-dependent density functional theory and analyzed resorting to the summation-over-states scheme. Besides confirming a β contrast of at least one order of magnitude, calculations point out the key role of the metal-to-ligand charge transfer state, which is responsible for the larger β response of the reduced Ru(II) form. Results also evidence the small contribution to β of the higher-energy intra-ligand charge transfer excited states, as well as the small changes of the depolarization ratio upon oxidation.

AB - The first hyperpolarizability (β) of [RuII-(NH 3)5(4-AcPhQ)]3+ and of its oxidized form [RuIII-(NH3)5(4-AcPhQ)]4+, previously synthesized and characterized by Coe and co-workers by means of hyper-Rayleigh scattering measurements, has been calculated using time-dependent density functional theory and analyzed resorting to the summation-over-states scheme. Besides confirming a β contrast of at least one order of magnitude, calculations point out the key role of the metal-to-ligand charge transfer state, which is responsible for the larger β response of the reduced Ru(II) form. Results also evidence the small contribution to β of the higher-energy intra-ligand charge transfer excited states, as well as the small changes of the depolarization ratio upon oxidation.

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U2 - 10.1016/j.cplett.2013.04.071

DO - 10.1016/j.cplett.2013.04.071

M3 - Article

AN - SCOPUS:84878573408

SN - 0009-2614

VL - 574

SP - 42

EP - 46

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Theoretical investigation of the first hyperpolarizability redox-switching in a ruthenium complex

Abstract

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