Linear and two-photon absorption properties of interacting polar chromophores: standard and unconventional effects

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
Francesca TerenzianiMireille Blanchard-Desce

Abstract

Investigations into the effects of electrostatic interactions on linear and two-photon absorption (TPA) properties are probed using a reference polar chromophore and different related compounds. Compounds in which a passive charge is present near the active chromophore, as well as dimers of the reference molecule, were studied. The combined experimental and theoretical investigation demonstrates that strong modulation of the properties can be attained. In particular, the TPA response of dimers is heavily affected by unconventional excitonic effects, that is, beyond the standard Heitler-London approximation. These effects, which stem from purely electrostatic interactions, lower the nonlinear optical response in the investigated case by an additional amount (up to 20%), and are expected to enhance the TPA cross section in other supramolecular alignments. Electrostatic interactions cannot be overlooked when modelling or investigating highly concentrated and/or confined samples, as are usually needed in many applications. The correct knowledge of their effects can be exploited to guide engineering at the molecular and supramolecular level.

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Citations

Oct 16, 2009·Physical Chemistry Chemical Physics : PCCP·Luca GrisantiRenato Bozio
Sep 26, 2009·The Journal of Chemical Physics·Masayoshi NakanoBenoît Champagne
Jan 1, 2008·The Journal of Chemical Physics·Lara FerrighiKenneth Ruud
Nov 5, 2014·The Journal of Chemical Physics·Cristina SissaAnna Painelli
Oct 15, 2009·Angewandte Chemie·Francesca TerenzianiMireille Blanchard-Desce
Nov 13, 2007·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Francesca TerenzianiAnna Painelli
Mar 28, 2007·Angewandte Chemie·Kenji KamadaMasayoshi Nakano
Feb 18, 2011·Chemistry, an Asian Journal·Valérie Alain-RizzoMireille Blanchard-Desce
Oct 10, 2013·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Małgorzata WielgusWojciech Bartkowiak
Feb 6, 2014·Advanced Materials·Emilie GeninMireille Blanchard-Desce
Apr 29, 2015·Physical Chemistry Chemical Physics : PCCP·F Terenziani, A Painelli
Jun 4, 2016·The Journal of Physical Chemistry. a·Josiah A BjorgaardSergei Tretiak
Jun 28, 2016·Chemistry : a European Journal·Eduardo Cueto DiazMireille Blanchard-Desce
Sep 21, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Cristiano MastrodonatoMireille Blanchard-Desce
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May 7, 2019·Chemical Science·Maxime KlausenMireille Blanchard-Desce
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Oct 11, 2019·Beilstein Journal of Organic Chemistry·Anne-Marie CaminadeMireille Blanchard-Desce
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Jun 28, 2019·Journal of Chemical Theory and Computation·Roberto Di RemigioLuca Frediani
Jan 30, 2007·The Journal of Physical Chemistry. a·Lian C T ShouteAnne Myers Kelley

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