Calculation and electronic description of quadratic hyperpolarizabilities. Toward a molecular understanding of NLO responses in organotransition metal chromophores

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Abstract

This contribution explores the use of the computationally efficient, chemically-oriented INDO electronic structure model (ZINDO) in concert with perturbation theory to relate molecular quadratic hyperpolarizabilities to molecular architecture and electronic structure in transition metal chromophores. The ZINDO-derived second-order nonlinear optical responses are found to be in excellent agreement with the experiment for a variety of ferrocenyl and (arene)chromium tricarbonyl derivatives. The assumptions needed to describe nonlinear optical response in simple molecular orbital terms are presented, and their reliability is analyzed in a quantitative fashion. All of the ferrocenyl chromophores examined are found to closely resemble traditional organic π-electron chromophores in that intense MLCT transitions dominate the second-order response. A detailed examination of the modest second-order nonlinearities of the chromium arenes identifies two shortcomings that may be characteristic of many organometallic architectures: the intrinsic hyperpolarizability may be far greater than the experimentally accessible vectorial component of β (that directed along the dipole moment direction), and the electronic distribution about the metal centers in many organometallic structures is pseudo-centrosymmetric. This explains the relatively low nonlinearities of a number of recently reported organometallic chromophores. The design utility of the present computational formalism is illustrated by the calculation of the second-order response of a hypothetical organometallic chromophore having a very acentric electron distribution and, correspondingly, a larger calculated second-order response than any measured to date for an organometallic chromophore.

Original languageEnglish
Pages (from-to)10338-10357
Number of pages20
JournalJournal of the American Chemical Society
Volume114
Issue number26
Publication statusPublished - 1992

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Chromium
Chromophores
Organometallics
Metals
Electrons
Electronic structure
Dipole moment
Molecular orbitals
Electron transitions
Transition metals
Derivatives
Direction compound
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "This contribution explores the use of the computationally efficient, chemically-oriented INDO electronic structure model (ZINDO) in concert with perturbation theory to relate molecular quadratic hyperpolarizabilities to molecular architecture and electronic structure in transition metal chromophores. The ZINDO-derived second-order nonlinear optical responses are found to be in excellent agreement with the experiment for a variety of ferrocenyl and (arene)chromium tricarbonyl derivatives. The assumptions needed to describe nonlinear optical response in simple molecular orbital terms are presented, and their reliability is analyzed in a quantitative fashion. All of the ferrocenyl chromophores examined are found to closely resemble traditional organic π-electron chromophores in that intense MLCT transitions dominate the second-order response. A detailed examination of the modest second-order nonlinearities of the chromium arenes identifies two shortcomings that may be characteristic of many organometallic architectures: the intrinsic hyperpolarizability may be far greater than the experimentally accessible vectorial component of β (that directed along the dipole moment direction), and the electronic distribution about the metal centers in many organometallic structures is pseudo-centrosymmetric. This explains the relatively low nonlinearities of a number of recently reported organometallic chromophores. The design utility of the present computational formalism is illustrated by the calculation of the second-order response of a hypothetical organometallic chromophore having a very acentric electron distribution and, correspondingly, a larger calculated second-order response than any measured to date for an organometallic chromophore.",
author = "Kanis, {David R.} and Ratner, {Mark A.} and Marks, {Tobin J.}",
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