Structure and Rearrangements of Carbocations. The Isotopic Perturbation Method

在这个项目中（“碳正离子的结构和重排”）。在有机动力学项目中，耶鲁大学化学系的Martin Saunders教授将继续研究同位素摄动法的发展和应用。这个项目的重点将是研究活性碳正离子的基本性质。本项目将重点扩展同位素摄动方法，研究多重氘化的协同效应，这种协同效应产生的平衡同位素效应是氘原子数的非线性函数。实验证据将从快速过程中同位素效应的角依赖性的研究中获得，这些过程包括围绕碳正离子轨道与碳氢键和碳碳键之间改变二面角的单键旋转。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.