title: Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene.
abstract: In this study we report on the electronic and vibrational (hyper)polarizabilities of donor-acceptor-substituted azobenzene. It is observed that both electronic and vibrational contributions to the electric dipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected density functional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange-correlation potentials amend the drawbacks of their conventional counterparts.
authors.affiliation: Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland. robert.zalesny@pwr.wroc.pl
authors.forename: Robert
authors.initials: R
authors.lastname: Zaleśny
authors.forename: Ireneusz W
authors.initials: IW
authors.lastname: Bulik
authors.forename: Wojciech
authors.initials: W
authors.lastname: Bartkowiak
authors.forename: Josep M
authors.initials: JM
authors.lastname: Luis
authors.forename: Aggelos
authors.initials: A
authors.lastname: Avramopoulos
authors.forename: Manthos G
authors.initials: MG
authors.lastname: Papadopoulos
authors.forename: Przemysław
authors.initials: P
authors.lastname: Krawczyk
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D003198:Computer Simulation; D004583:Electrons; D015394:Molecular Structure; D014732:Vibration
chemical_list: D001391:Azo Compounds; C009850:azobenzene