Charge distribution and second-order nonlinear optical response of charged centrosymmetric chromophore aggregates. An ab initio electronic structure study of p-nitroaniline dimers

Santo Di Bella, Giuseppe Lanza, Ignazio Fragalà, Shlomo Yitzchaik, Mark A Ratner, Tobin J Marks

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

This contribution presents a quantum chemical investigation of the nonlinear optical response of charged centrosymmetric aggregates of the archetypical chromophore p-nitroaniline using an ab initio supermolecular approach. Localized hole states, responsible for aggregate nonlinearity, are predicted to be more stable than delocalized states. The calculated aggregate hyperpolarizabilities are consistently larger than in the isolated chromophore, and the mechanism giving rise to the nonlinearly is essentially 'intramolecular' in nature. The aggregate formation is predicted to stabilize the positive charge and to enhance the nonlinearity. Moreover, the calculations reveal that a (formally) centrosymmetric charged aggregate can possess a substantial dipole moment the principal axis of which is oriented perpendicular to the principal hyperpolarizability tensor; the dipole moment arises because electron localization breaks the charge distribution symmetry. These results explain a number curious features of chromophoric polymer films which are electric field poled with an 'in-plane' electrode geometry.

Original languageEnglish
Pages (from-to)3003-3006
Number of pages4
JournalJournal of the American Chemical Society
Volume119
Issue number13
DOIs
Publication statusPublished - Apr 2 1997

Fingerprint

Charge distribution
Chromophores
Dimers
Electronic structure
Polymers
Electrodes
Electrons
Dipole moment
Polymer films
Tensors
Electric fields
4-nitroaniline
Geometry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Charge distribution and second-order nonlinear optical response of charged centrosymmetric chromophore aggregates. An ab initio electronic structure study of p-nitroaniline dimers. / Di Bella, Santo; Lanza, Giuseppe; Fragalà, Ignazio; Yitzchaik, Shlomo; Ratner, Mark A; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 119, No. 13, 02.04.1997, p. 3003-3006.

Research output: Contribution to journalArticle

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AU - Fragalà, Ignazio

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AU - Ratner, Mark A

AU - Marks, Tobin J

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AB - This contribution presents a quantum chemical investigation of the nonlinear optical response of charged centrosymmetric aggregates of the archetypical chromophore p-nitroaniline using an ab initio supermolecular approach. Localized hole states, responsible for aggregate nonlinearity, are predicted to be more stable than delocalized states. The calculated aggregate hyperpolarizabilities are consistently larger than in the isolated chromophore, and the mechanism giving rise to the nonlinearly is essentially 'intramolecular' in nature. The aggregate formation is predicted to stabilize the positive charge and to enhance the nonlinearity. Moreover, the calculations reveal that a (formally) centrosymmetric charged aggregate can possess a substantial dipole moment the principal axis of which is oriented perpendicular to the principal hyperpolarizability tensor; the dipole moment arises because electron localization breaks the charge distribution symmetry. These results explain a number curious features of chromophoric polymer films which are electric field poled with an 'in-plane' electrode geometry.

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