作者: Jing Huang , Markus Meuwly
DOI: 10.1002/9783527658824.CH10
关键词: Chemical physics 、 Intramolecular force 、 Computational chemistry 、 Quantum 、 Intermolecular force 、 Molecular dynamics 、 Observable 、 Force field (chemistry) 、 Chemistry 、 QM/MM 、 Basis set
摘要: Proton and hydrogen-bonded motifs are amongst the most widely occurring patterns in chemistry biology. Besides their intrinsic chemical significance, they also display a fascinating range of dynamical effects including highly quantum behavior or strong coupling between inter intramolecular degrees freedom. In biological systems, rates for proton transfer (PT) hydrogen (HT) can cover picosecond to millisecond range, which corresponds few kilocalories per mole up 20 kcal mol−1. From computational perspective, this implies that energetics along specific motif has be extensively sampled order converge experimental observables. Possible approaches treat include ab initio molecular dynamics (AIMD) simulations, mixed mechanical/molecular mechanics (QM/MM) calculations, more less empirical parameterizations intermolecular interactions based on model potentials parameterized fits rigorous calculations. chapter, we discuss QM/MM embedding schemes into an force field fitting high-quality (Moller–Plesset perturbation theory (MP2) with large basis set) allows explicit treatment long-time dynamics. The essential feature procedure is its accuracy, flexibility, suitability either QM classical treatments nuclear present chapter discusses theory, implementation, applications scheme it regard other existing ways PT HT strongly weakly coupled systems. reactions fundamental Although famous Grotthuss shuttling mechanism [1] was introduced than 200 years ago, notable progress understanding atomistic details underlying process only been achieved recently modern spectroscopic techniques high-performance computer simulations [2]. point view, infrared (IR) studies [3–5] were successful probing vibrational bonds. However, complete assignment/interpretation spectra