Gaigeot Marie-Pierre, Spezia Riccardo
LAMBE UMR 8587, Université d'Evry-Val-d'Essonne, Paris, France,
Top Curr Chem. 2015;364:99-151. doi: 10.1007/128_2014_620.
In this chapter we review recent advances in theoretical methods to understand and rationalize anharmonic vibrational spectroscopy (IR-MPD and IR-PD) and collision induced dissociations (CID) in the gas phase. We focused our attention on the application of molecular dynamics-based methods. DFT-based molecular dynamics was shown to be able to reproduce InfraRed Multi-Photon Dissociation (IR-MPD) and InfraRed Pre-Dissociation (IR-PD) action spectroscopy experiments, and help assign the vibrational bands, taking into account finite temperature, conformational dynamics, and various anharmonicities. Crucial examples of dynamical vibrational spectroscopy are given on the protonated Ala n H(+) series (related to IR-MPD in the 800-4,000 cm(-1) domain), ionic clusters (related to IR-PD in the 3,000-4,000 cm(-1) region), and neutral peptides (related to IR-MPD in the far-IR). We give examples from simple (e.g., cationized urea) to more complex (e.g., peptides and carbohydrates) molecular systems where molecular dynamics was particularly suited to understanding CID experiments.
在本章中，我们回顾了用于理解和阐释气相中非谐振动光谱（红外多光子解离和红外预解离）以及碰撞诱导解离的理论方法的最新进展。我们将注意力集中在基于分子动力学的方法的应用上。基于密度泛函理论的分子动力学已被证明能够重现红外多光子解离（IR-MPD）和红外预解离（IR-PD）作用光谱实验，并有助于在考虑有限温度、构象动力学和各种非谐性的情况下对振动带进行归属。在质子化丙氨酸系列（与800 - 4000 cm⁻¹ 范围内的IR-MPD相关）、离子簇（与3000 - 4000 cm⁻¹ 区域内的IR-PD相关）和中性肽（与远红外区的IR-MPD相关）上给出了动态振动光谱的关键示例。我们给出了从简单分子体系（如阳离子化尿素）到更复杂分子体系（如肽和碳水化合物）的示例，其中分子动力学特别适合于理解碰撞诱导解离实验。
