The influence of solvent on the two-photon absorption cross section and hyperpolarizability of molecules exhibiting large solvatochromic shifts

Issue title: Computational aspects of electric polarizability calculations: Atoms, Molecules and clusters Part II

Article type: Research Article

Authors: Bartkowiak, Wojciech^{a; *} | Skwara, Bartłomiej^a | Zaleśny, Robert^{a; b}

Affiliations: [a] Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, Wyb. Wyspiańskiego 27, 50-370 Wroclaw, Poland | [b] Department of Quantum Chemistry, Institute of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100, Toruń, Poland

Correspondence: [*] Corresponding author. Tel.: +48 71 320-26-75; Fax: +48 71 320 33 64; E-mail: bartkowiak@kchf.ch.pwr.wroc.pl.

Abstract: A theoretical approach to the effect of influence of solute/solvent interaction on the electronic contributions to the two-photon absorption cross section (δ) is presented. The solvent effect was included via a discrete quantum-mechanical Langevin dipoles/Monte Carlo method. The calculations of δ were performed for the first excited singlet state connected with the intramolecular charge transfer (CT). The results of calculations demonstrate the existence of the significant solvent effect on the two-photon absorption cross section (δ) of the charge-transfer chromophore (p-nitroaniline) exhibiting large solvatochromic shifts. The results of quantum-chemical calculations are analyzed based on the simple two-state model.

Keywords: Two-photon absorption, solvent effect, hyperpolarizability, p-nitroaniline

DOI: 10.3233/JCM-2004-4402

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 4, no. 4, pp. 551-558, 2004