Giovannini Tommaso, Gómez Sara, Cappelli Chiara
Department of Physics and INFN, University of Rome Tor Vergata, Via della Ricerca Scientifica 1, 00133 Rome, Italy.
Departamento de Química, Universidad Nacional de Colombia, Av. Cra 30 45-03, 111321 Bogotà, Colombia.
J Phys Chem Lett. 2025 Mar 27;16(12):3106-3121. doi: 10.1021/acs.jpclett.4c03591. Epub 2025 Mar 18.
This perspective highlights the essential physicochemical factors required for accurate computational modeling of Raman and Resonance Raman signals in complex environments. It highlights the theoretical challenges for obtaining a balanced quantum mechanical description of the molecular target, integration of target-environment interactions into the Hamiltonian, and explicit treatment of strong interactions such as hydrogen bonding. The dynamical sampling of solute-solvent phase space and the incorporation of plasmonic effects for Surface-Enhanced Raman Scattering (SERS) are also addressed. Through selected applications, we illustrate how these factors influence Raman signals and propose a framework to tackle these challenges effectively, advancing the reliability of theoretical Raman spectroscopy in real-world scenarios.
这一观点强调了在复杂环境中对拉曼和共振拉曼信号进行精确计算建模所需的基本物理化学因素。它突出了在获得分子靶标的平衡量子力学描述、将靶标 - 环境相互作用纳入哈密顿量以及明确处理诸如氢键等强相互作用方面的理论挑战。还讨论了溶质 - 溶剂相空间的动态采样以及表面增强拉曼散射（SERS）的等离子体效应的纳入。通过选定的应用，我们说明了这些因素如何影响拉曼信号，并提出了一个有效应对这些挑战的框架，从而提高理论拉曼光谱在实际场景中的可靠性。
