Theoretical Chemistry Group, Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, 50-370 Wrocław, Poland.
J Chem Phys. 2010 Dec 28;133(24):244308. doi: 10.1063/1.3516209.
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.
在这项研究中，我们报告了供体-受体取代偶氮苯的电子和振动（超）极化率。研究发现，所研究的光活性分子的电偶极第一超极化率的电子和振动贡献都极大地依赖于构象。对于所考虑的两种异构体（顺式和反式），发现核弛豫第一超极化率的贡献相当重要。虽然双调和项在幅度上是最大的，但结果表明，核弛豫对振动第一超极化率的贡献的总价值是各种高阶贡献相互作用的结果。作为研究的一部分，我们还评估了长程校正密度泛函理论在确定电偶极（超）极化率的振动贡献方面的性能。在大多数情况下，所应用的长程校正交换相关势弥补了它们的常规对应物的缺点。
