Ultraviolet resonance Raman (UVRR) scattering is a highly sensitive and selective vibrational spectroscopic technique with a broad range of applications from polyaromatic hydrocarbons (PAHs) to biomolecular systems (peptides/proteins and nucleic acids) and catalysts. The interpretation of experimental UVRR spectra is not as straightforward as in purely vibrational Raman scattering (Placzek approximation) due to the involvement of higher lying electronic states and vibronic coupling. This necessitates the comparison with theoretical UVRR spectra computed by electronic structure calculations. Anthracene is an ideal model system for such a comparison between experiment and theory because it is rigid, symmetric, and of moderate size. By taking into account Herzberg–Teller contributions including Duschinsky effects, bulk solvent effects, and anharmonic contributions, a good qualitative agreement close to the resonance condition is achieved. The present study shows that within the framework of time-dependent density functional theory (TD-DFT), a general and robust approach for the analysis and interpretation of resonance Raman spectra of medium- to large-size molecules is available.

中文翻译：

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蒽的紫外共振拉曼光谱：实验与理论

紫外共振拉曼 (UVRR) 散射是一种高灵敏度和选择性的振动光谱技术，具有广泛的应用，从多环芳烃 (PAH) 到生物分子系统（肽/蛋白质和核酸）和催化剂。由于涉及更高的电子态和振动耦合，实验 UVRR 光谱的解释不像纯振动拉曼散射（Placzek 近似）那样简单。这需要与通过电子结构计算计算出的理论 UVRR 光谱进行比较。蒽是进行这种实验与理论比较的理想模型系统，因为它刚性、对称且大小适中。通过考虑 Herzberg-Teller 的贡献，包括 Duschinsky 效应、本体溶剂效应，和非谐波贡献，实现了接近共振条件的良好定性一致性。本研究表明，在瞬态密度泛函理论 (TD-DFT) 的框架内，可以使用一种通用且稳健的方法来分析和解释大中分子的共振拉曼光谱。