Efficient simulation of overtones and combination bands in resonant Raman spectra
Efficient simulation of overtones and combination bands in resonant Raman spectra
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DOI：
10.1063/1.5099247
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发表时间：
2019-06-07
影响因子：
4.4
通讯作者：
Izsak, Robert
中科院分区：
文献类型：
--
作者：
de Souza, Bernardo;Farias, Giliandro;Izsak, Robert
在这项工作中，我们描述了如何使用谐振子的路径积分公式，包括Herzberg-Teller和Duschinsky旋转效应，以良好的精度预测共振拉曼（RR）光谱。特别是，我们将专注于近似值，以使这些计算更有效，并扩展当前的方法，在最终预测中包括泛音和组合带。在概述了理论之后，我们解释了如何将其制成黑盒方法，并讨论了依赖于其固有参数的近似值。结果表明，后者可以在精度没有明显损失的情况下，将效率提高几个数量级。我们还将证明，即使在高阶振动激励下，预测的RR光谱在光谱峰的强度和位置上都与实验结果吻合得很好。因此，本文提出的方法可以作为实验的计算辅助，以提高分析质量和对RR的理论认识。
In this work, we describe how Resonant Raman (RR) spectra can be predicted with good accuracy using the path integral formulation for the harmonic oscillator, including the Herzberg-Teller and Duschinsky rotation effects. In particular, we will focus on approximations to make these calculations more efficient and expand the current methodology to include overtones and combination bands in the final prediction. After outlining the theory, we explain how it can be made into a black-box method and discuss the approximations that rely on its intrinsic parameters. It is shown that the latter can improve the efficiency by orders of magnitude, without substantial loss in accuracy. We will also show that the predicted RR spectra are in good agreement with experiment for both the intensity and position of spectral peaks, even for higher order vibronic excitations. Thus, the method proposed here can be used as a computational aid to experiments to improve the quality of analysis and theoretical understanding of RR.