An electrostatic model for the energetics of large heterocluster cations

Narda Ben-Horin, Hanoch Sanderovitch, Uzi Kaldor, Uzi Even, Joshua Jortner

Research output: Contribution to journalArticlepeer-review

Abstract

In this paper we extend and apply the electrostatic model [Jortner, J.; Even, U.; Leutwyler, S.; Berkowitch-Yellin, Z. J. Chem. Phys. 1983, 78, 305] for the calculation of the ionization potentials of M·An heteroclusters (M = benzene, anthracene (ANT) and 9,10-dichloroanthracene (DCA); A = Ar and Kr). The electrostatic contributions to the ionization potential shift δΙ of the heterocluster relative to the bare molecule (consisting of charge-induced dipole and induced dipole-induced dipole M+-An and M-An interactions) were evaluated using the entire π and σ atomic charge densities of M+ and of M. Molecular wave functions for ANT, for DCA, and for their cations were computed using the semiempirical MNDO method and utilized for the computation of the atomic charges by the Mulliken and the Löwdin methods. The Löwdin charges provide the best description of δΙ. The modification of the calculated δΙ for benzene·Ar by the improvement of the molecular wave functions for benzene+ and benzene was also explored. The electrostatic model, together with structural data, accounts for the experimental δΙ data of benzene·Ar1, ANT·Ar1, ANT·Kr1, DCA·Ar1, and DCA·Kr1. The electrostatic model in conjunction with finite temperature molecular dynamics simulations accounts well for the size dependence of δΙ for DCA·Arn and DCA·Krn (n = 1-18) heteroclusters.

Original languageEnglish
Pages (from-to)1569-1575
Number of pages7
JournalJournal of Physical Chemistry
Volume96
Issue number4
DOIs
StatePublished - 1992

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