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Updated: Jun 5, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene
Robert Zaleśny1, Ireneusz W Bulik, Wojciech Bartkowiak
1Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland. robert.zalesny@pwr.wroc.pl
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.
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