Nonlinear optical property calculations by the long-range-corrected coupled-perturbed Kohn-Sham method

Muneaki Kamiya; Hideo Sekino; Takao Tsuneda; Kimihiko Hirao

doi:10.1063/1.1935514

Nonlinear optical property calculations by the long-range-corrected coupled-perturbed Kohn-Sham method

J Chem Phys. 2005 Jun 15;122(23):234111. doi: 10.1063/1.1935514.

Authors

Muneaki Kamiya¹, Hideo Sekino, Takao Tsuneda, Kimihiko Hirao

Affiliation

¹ Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan.

PMID: 16008434
DOI: 10.1063/1.1935514

Abstract

The long-range correction (LC) scheme for the exchange functional of density-functional theory (DFT) was combined with the coupled-perturbed Kohn-Sham (CPKS) method to calculate nonlinear optical response properties. By using this LC-CPKS method, we calculated the hyperpolarizabilities of typical molecules and the dipole moments, polarizabilities, and hyperpolarizabilities of push-pull pi-conjugated systems: p-nitroaniline, 4-amino-4'-nitrostilbene, and alpha,omega-nitroaminopolyenes. It was found that the LC scheme clearly improved the calculation of these optical properties for all of these systems, which have been significantly overestimated by conventional DFTs. We therefore concluded that the long-range exchange interaction played an important role in calculating the optical properties using the DFT formalism.