Mechanisms of solvation dynamics of polyatomic solutes in polar and nondipolar solvents: A simulation study
Mechanisms of solvation dynamics of polyatomic solutes in polar and nondipolar solvents: A simulation study
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极性和非偶极溶剂中多原子溶质的溶剂化动力学机制：模拟研究
DOI：
10.1063/1.476911
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发表时间：
1998
影响因子：
4.4
通讯作者：
M. Maroncelli
中科院分区：
文献类型：
--
作者：
B. Ladanyi;M. Maroncelli
用分子动力学（MD）方法模拟了苯类溶质在乙腈和CO2（298 K和52.18 cm 3/mol）中的溶剂化动力学，研究了极性和非偶极溶剂中溶剂化动力学的分子基础.溶剂化反应的苯溶质内的各种电荷重排进行了模拟，以模仿在典型的实验系统中观察到的静电溶剂化的类型。从平衡态分子动力学模拟的溶剂化时间相关函数[TCF; C（t）]和相应的溶剂化速度TCF [G（t）]被用来研究在线性响应极限内的时间依赖性溶剂化的机制。将G（t）分解为旋转和平移溶剂速度的贡献揭示了这两种类型的运动的相对混合在两种溶剂中非常相似，但强烈依赖于溶质扰动的多极阶（m）。平移溶剂运动的贡献的短期和长期动态的C（t）增加…
Molecular dynamics (MD) simulations of a benzenelike solute in acetonitrile and CO2 (298 K and 52.18 cm3/mol) are used to investigate the molecular basis of solvation dynamics in polar and nondipolar solvents. The solvation response to various charge rearrangements within the benzene solute are simulated in order to mimic the type of electrostatic solvation observed in typical experimental systems. From equilibrium MD simulations the solvation time correlation function [TCF; C(t)] and the corresponding solvation velocity TCF [G(t)] are used to study the mechanisms underlying time-dependent solvation within the linear response limit. Decomposition of G(t) into contributions from rotational and translational solvent velocities reveals that the relative mix of these two types of motion is quite similar in the two solvents but is strongly dependent on the multipolar order (m) of the solute perturbation. The contribution of translational solvent motions to both the short and long time dynamics of C(t) increase...