Can aromaticity be connected with molecular polarizability? A theoretical study of benzene isomers and five-membered heterocyclic molecules

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

Article type: Research Article

Authors: Jartín, R. Soriano^a | Cuesta, I. García^b | Sánchez de Merás, A.^b | Lazzeretti, P.^{a; *}

Affiliations: [a] Dipartimento di Chimica dell'Università degli Studi di Modena e Reggio Emilia, Via Campi 183, 41100 Modena, Italy | [b] Departament de Química Física, Institut de Ciència Molecular, Universitat de València, Carrer Dr. Moliner 50, 46100 Burjassot, València, Spain

Correspondence: [*] Corresponding author. E-mail: [email protected].

Abstract: Extended calculations of molecular electric dipole polarizability tensor, at Hartree-Fock and correlated level of accuracy (MP2, CCS, CC2, CCSD, and CCSD(T)) have been carried out to investigate whether aromaticity could be related to the electric dipole polarizability of planar ring systems. The calculations prove the exaltation of the average property of conjugated molecules, which is possibly due to their easily polarizable π-electron cloud. On the other hand, theoretical out-of-plane polarizability components are smaller in benzene than in any other C6H6 isomer. The aromatic stabilization energies of monosubstituted five-membered conjugated cyclic molecules increase in the same direction as theoretical out-of-plane polarizabilities.

Keywords: molecular electric polarizabilites, aromaticity, MP2 and coupled cluster correlation contributions, pentatomic heterocyclic molecules

DOI: 10.3233/JCM-2004-4409

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 4, no. 4, pp. 665-676, 2004