Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)

作者：Hongfei Wang, Wei Gan, Rong Lu † ‡ §, Yi Rao, Baohua Wu · 发表于：International Reviews in Physical Chemistry · 年份：2005 · DOI：10.1080/01442350500225894 · 被引用次数：769 · 研究领域：Spectroscopy and Quantum Chemical Studies、Thermodynamic properties of mixtures、Advanced Chemical Physics Studies

Sum frequency generation vibrational spectroscopy (SFG-VS) has been proven to be a uniquely effective spectroscopic technique in the investigation of molecular structure and conformations, as well as the dynamics of molecular interfaces. However, the ability to apply SFG-VS to complex molecular interfaces has been limited by the ability to abstract quantitative information from SFG-VS experiments. In this review, we try to make assessments of the limitations, issues and techniques as well as methodologies in quantitative orientational and spectral analysis with SFG-VS. Based on these assessments, we also try to summarize recent developments in methodologies on quantitative orientational and spectral analysis in SFG-VS, and their applications to detailed analysis of SFG-VS data of various vapour/neat liquid interfaces. A rigorous formulation of the polarization null angle (PNA) method is given for accurate determination of the orientational parameter D = ⟨cos θ ⟩/⟨cos3 θ⟩, and comparison between the PNA method with the commonly used polarization intensity ratio (PIR) method is discussed. The polarization and incident angle dependencies of the SFG-VS intensity are also reviewed, in the light of how experimental arrangements can be optimized to effectively abstract crucial information from the SFG-VS experiments. The values and models of the local field factors in the molecular layers are discussed. In order to examine the validity and limitations of the bond polarizability deri...