Structure and Rearrangements of Carbocations. The Isotopic Perturbation Method

在有机动力学计划的这个项目(碳正离子的结构和重排。同位素微扰法)中，耶鲁大学化学系的马丁·桑德斯教授将继续研究同位素微扰法的发展和应用。本项目的重点将是研究反应性碳正离子的基本性质。这个项目将集中在同位素微扰方法的扩展上，以研究多个氚原子产生的平衡同位素效应的协同效应，这些平衡同位素效应是氚原子数量的非线性函数。对快速过程中同位素效应的角度依赖性的研究将获得实验证据，这些快速过程包括围绕改变碳正离子轨道和碳-氢和碳-碳键之间的二面角的单键旋转。我们将进行从头算量子力学计算来预测碳正离子的能量和结构，并预测平衡同位素效应，并将其与实验结果进行比较。

In this project ("Structure and Rearrangement of Carbocations. The Isotopic Perturbation Method") in the Organic Dynamics Program, Professor Martin Saunders of the Chemistry Department at Yale University will continue studies on the development and applications of the isotopic perturbation method. The focus of this project will be the investigation of the fundamental properties of reactive carbocations. This project will be focussed on the extension of the isotopic perturbation method to study the cooperative effects of multiple deuteration which produces equilibrium isotope effects that are nonlinear functions of the number of deuterium atoms. Experimental evidence will be obtained from investigations of the angular dependence of the isotope effects in rapid processes which include rotation around single bonds that varies dihedral angles between carbocation orbitals and carbon-hydrogen and carbon-carbon bonds. Ab initio quantum mechanical calculations will be performed to predict the energies and structures of carbocations and to predict equilibrium isotope effects which will be compared with the experimental results.