期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 125, 期 5, 页码 1243-1256出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.0c11356
关键词
-
资金
- U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [DE-SC0008550]
- Ohio State University
- Ohio Supercomputer Center [PAA-0003.118]
Binary halide-water complexes X-(H2O) were studied using symmetry-adapted perturbation theory, revealing that charge-transfer energy is small but crucial in determining conformational preferences and driving the formation of hydrogen bonds.
Binary halide-water complexes X-(H2O) are examined by means of symmetry-adapted perturbation theory, using charge-constrained promolecular reference densities to extract a meaningful charge-transfer component from the induction energy. As is known, the X-(H2O) potential energy surface (for X = F, Cl, Br, or I) is characterized by symmetric left and right hydrogen bonds separated by a C-2v-symmetric saddle point, with a tunneling barrier height that is <2 kcal/mol except in the case of F-(H2O). Our analysis demonstrates that the charge-transfer energy is correspondingly small (<2 kcal/mol except for X = F), considerably smaller than the electrostatic interaction energy. Nevertheless, charge transfer plays a crucial role determining the conformational preferences of X-(H2O) and provides a driving force for the formation of quasi-linear X center dot center dot center dot H-O hydrogen bonds. Charge-transfer energies correlate well with measured O-H vibrational redshifts for the halide-water complexes and also for OH-(H2O) and NO2-(H2O), providing some indication of a general mechanism.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据