An ab initio time-dependent Hartree-Fock study of solvent effects on the polarizability and second hyperpolarizability of polyacetylene chains within the polarizable continuum model

Benoît Champagne, Benedetta Mennucci, Maurizio Cossi, Roberto Cammi, Jacopo Tomasi

Research output: Contribution to journalArticlepeer-review

Abstract

The solvent effects upon the longitudinal polarizability (αL) and second hyperpolarizability (γL) of small all-trans polyacetylene (PA) chains ranging from C2H4 to C10H12 have been evaluated at the time-dependent Hartree-Fock (TDHF) level within the framework of the polarizable continuum model. The solvent effects, which correspond to the solvent-induced modifications of the solute properties, result in large increases of the linear and nonlinear responses even for solvents with low dielectric constants. When the dielectric constant is increased, the αL values tend to saturate at values 30%-40% larger than in vacuo, whereas for γL it ranges from 100% to 400% depending upon the nonlinear optical process and the length of the PA chain. These solvent-induced αL and γL enhancements can partially be accounted for by the corresponding decrease of the energy of the lowest optically-allowed electronic excitation. The geometrical parameters of the ground state of the PA chains are almost unaffected by the solvent. This shows that the solvent effects are mainly of electronic nature. In addition, the local field factors, which relate the macroscopic or Maxwell field to the field experienced by the solute, tend towards unity with increasing chain length for the longitudinal PA axis.

Original languageEnglish
Pages (from-to)153-163
Number of pages11
JournalChemical Physics Letters
Volume238
Issue number2
Publication statusPublished - 15 Nov 1998

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