Large Dispersion Effects in Organic and Organometallic Thermochemistry, Stereochemistry, and Reaction Mechanisms

本项目研究了两种结构类型的分子，以第一相为特征，其气相键能和相应的溶液平衡可以通过实验来测量。有了广泛的取代基，分散对键强度和平衡的影响可以被量化，并与有或没有隐式溶剂化模型的量子化学计算进行比较。这些结果适用于所有的成键或断键过程，即所有的化学反应，它们对现有理论模型的充分性提供了严格的检验。

This project investigates two structural classes of molecules, characterized in the first phase, for which gas-phase bond energies and the corresponding equilibria in solution can be measured experimentally. With a wide range of substituents, the effect of dispersion on the bond strengths and equilibria can be quantified and compared to quantum chemical calculations with and without implicit solvation models. The results are general for all bond-making or bond-breaking processes, i.e. all chemical reactions, and they provide a rigorous test of the adequacy of present theoretical models.