The vibronic theory of resonance hyper‐Raman scattering
The vibronic theory of resonance hyper‐Raman scattering
复制标题
共振超拉曼散射的电子理论
DOI：
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发表时间：
1988
期刊：
影响因子：
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通讯作者：
L. Ziegler
中科院分区：
文献类型：
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作者：
Y. Chung;L. Ziegler
振动共振超拉曼跃迁的强度是在电子振动理论的通常框架中发展的。与线性拉曼散射类似，当跃迁超极化率中的电子跃迁矩展开到核坐标依赖的一阶时，发现了RHR散射的主导项A、B和C。非中心对称分子被预测为最强的非线性散射体，并从RHR A项获得活性。与线性拉曼散射的电子振动分析相反，对于中心对称分子，单光子和双光子允许跃迁都以相同的电子振动理论阶数（B项）对RHR散射截面做出贡献。气相CH 3 I、NH3和CS2的RHR散射光谱说明了A-和B-项RHR活性。
The intensities of vibrational resonance hyper‐Raman transitions are developed in the usual framework of vibronic theory. In analogy to linear Raman scattering, the leading terms of RHR scattering, A, B, and C, are found when the electronic transitions moments, appearing in the transition hyperpolarizability, are expanded to first order in nuclear coordinate dependence. Noncentrosymmetric molecules are predicted to be the strongest nonlinear scatterers and derive activity from the RHR A term. In contrast to the vibronic analysis of linear Raman scattering, both one and two‐photon allowed transitions contribute to RHR scattering cross section at the same order of vibronic theory (B term) for centrosymmetric molecules. RHR scattering spectra of gas phase CH3I, NH3, and CS2 illustrate A‐ and B‐term RHR activity.