Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients
2014 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 141, no 13, 134107- p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2014. Vol. 141, no 13, 134107- p.
Other Chemistry Topics Atom and Molecular Physics and Optics
IdentifiersURN: urn:nbn:se:kth:diva-156453DOI: 10.1063/1.4896606ISI: 000343872800011ScopusID: 2-s2.0-84907835031OAI: oai:DiVA.org:kth-156453DiVA: diva2:767490
QC 201412012014-12-012014-11-282014-12-01Bibliographically approved