Rich Dynamics Underlying Solution Reactions Revealed by Sampling and   Data Mining of Reactive Trajectories

doi:10.1021/acscentsci.7b00037

CORC > 北京大学 > 化学与分子工程学院

	Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories
	Zhang, Jun ; Zhang, Zhen ; Yang, Yi Isaac ; Liu, Sirui ; Yang, Lijiang ; Gao, Yi Qin
刊名	ACS CENTRAL SCIENCE
	2017
关键词	CHEMICAL-REACTIONS CLAISEN REARRANGEMENT TRANSITION-STATES ORGANIC-SYNTHESIS IN-WATER ISOMERIZATION MECHANICS BARRIER PROTEIN MOTION
DOI	10.1021/acscentsci.7b00037
英文摘要	Efficient sampling in both configuration and trajectory spaces, combined with mechanism analyses via data mining, allows a systematic investigation of the thermodynamics, kinetics, and molecular-detailed dynamics of chemical reactions in solution. Through a Bayesian learning algorithm, the reaction coordinate(s) of a (retro-)Claisen rearrangement in bulk water was variationally optimized. The bond formation/breakage was found to couple with intramolecular charge separation and dipole change, and significant dynamic solvent effects manifest, leading to the "in water" acceleration of Claisen rearrangement. In addition, the vibrational modes of the reactant and the solvation states are significantly coupled to the reaction dynamics, leading to heterogeneous and oscillatory reaction paths. The calculated reaction rate is well interpreted by the Kramers' theory with a diffusion term accounting for solvent-solute interactions.These findings demonstrated that the reaction mechanisms can be complicated in homogeneous solutions since the solvent solute interactions can profoundly influence the reaction dynamics and the energy transfer process.; Natural Science Foundation of China [91427304, 21573006, 21373016, U1430237]; SCI(E); ARTICLE; 5; 407-414; 3
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/473637]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Zhang, Jun,Zhang, Zhen,Yang, Yi Isaac,et al. Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories[J]. ACS CENTRAL SCIENCE,2017.
APA	Zhang, Jun,Zhang, Zhen,Yang, Yi Isaac,Liu, Sirui,Yang, Lijiang,&Gao, Yi Qin.(2017).Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories.ACS CENTRAL SCIENCE.
MLA	Zhang, Jun,et al."Rich Dynamics Underlying Solution Reactions Revealed by Sampling and Data Mining of Reactive Trajectories".ACS CENTRAL SCIENCE (2017).