Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

作者：Ringholm Magnus^*; Bast Radovan; Oggioni Luca; Ekstrom Ulf; Ruud Kenneth

来源：Journal of Chemical Physics, 2014, 141(13): 134107.

DOI：10.1063/1.4896606

We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields, reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.

• 出版日期2014-10-7