title: Density-functional theory (hyper)polarizabilities of push-pull pi-conjugated systems: treatment of exact exchange and role of correlation.
abstract: The performance of the optimized effective potential procedure for exact exchange in calculating static electric-field response properties of push-pull pi-conjugated systems has been studied, with an emphasis on NO2-(CH=CH)n-NH2 chains. Good agreement with Hartree-Fock dipole moments and (hyper)polarizabilities is obtained; particularly noteworthy is the chain length dependence for beta/n. Thus, the problem that conventional density-functional theory functionals dramatically overestimate these properties is largely solved, although there remains a significant correlation contribution that cannot be accounted for with current correlation functionals.
authors.affiliation: Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile.
authors.forename: Felipe A
authors.initials: FA
authors.lastname: Bulat
authors.forename: Alejandro
authors.initials: A
authors.lastname: Toro-Labbé
authors.forename: Benoît
authors.initials: B
authors.lastname: Champagne
authors.forename: Bernard
authors.initials: B
authors.lastname: Kirtman
authors.forename: Weitao
authors.initials: W
authors.lastname: Yang