title: Theoretical investigation of quadrupole contributions to surface sum-frequency vibrational spectroscopy.
abstract: We study the effect of electric transition quadrupole moments on surface sum-frequency vibrational spectroscopy (SFVS). The SSP, PPP and SPS effective sum-frequency susceptibilities are derived from the nonzero macroscopic susceptibility tensors and related to molecular quadrupole polarizabilities. Using time-dependent density functional theory, we calculate the quadrupole susceptibilities of R-limonene liquids for the first time. The results indicate that quadrupole contributions have a significant influence on SFVS transmitted signals in the SPS polarization combination. We also suggest that the SPS spectra may be used as a general technique for detecting electric transition quadrupole moments.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun, Beijing 100190, P. R. China. zrh@iccas.ac.cn.
authors.forename: Ren-hui
authors.initials: RH
authors.lastname: Zheng
authors.forename: Wen-mei
authors.initials: WM
authors.lastname: Wei
authors.forename: Qiang
authors.initials: Q
authors.lastname: Shi
mesh_terms: D053138:Cyclohexenes / Q000737:chemistry*; D000077222:Limonene; D008962:Models, Theoretical; D011789:Quantum Theory; D013059:Spectrum Analysis, Raman / Q000379:methods*; D013499:Surface Properties; D013729:Terpenes / Q000737:chemistry*; D014732:Vibration
chemical_list: D053138:Cyclohexenes; D013729:Terpenes; D000077222:Limonene