Modern Theoretical Carbocation Chemistry

NSF化学部的化学结构，动力学和机制计划支持加州大学戴维斯分校化学系Dean Tantillo教授的研究。 Tantillo教授和他的学生正在使用现代计算化学方法来探索控制化学反应性的新原理。 揭示的原理改变了有机化学家如何预测导致复杂分子的许多反应的机制和产物分布。 除了通过这项研究发现的机械模型的根本重要性之外，该项目还用于培训来自不同背景的学生，使他们能够采用多学科方法进行机械化学，并使他们接触到采用这种技术的职业。 此外，正在开发使盲人和视障学生能够使用应用计算化学的新方法，作为鼓励这一群体在STEM领域从事职业的努力的一部分。这项研究的结果是传播，部分，通过与当地arboretum.This研究通过构建详细的碳阳离子反应机理模型的合作伙伴关系，在机械有机化学知识的进步推广计划。 特别是，不寻常的势能表面的碳阳离子重排的特点，非统计的动态影响碳阳离子的行为进行了分析和预测，模型的反应性被推到新的反应的设计和测试。本项目的具体目标是：（1）阐明控制多个异步事件协同反应中物种动力学行为的一般原理;（2）设计一个具有后过渡态分岔的反应，并在实验室实验之前预测其产物分布。(3)将theozyme动力学方法发展成为理解和设计利用相对较弱的非共价相互作用的催化剂的工具。

The Chemical Structure, Dynamics and Mechanism Program of the NSF Chemistry Division supports the research of Professor Dean Tantillo in the Department of Chemistry at The University of California-Davis. Professor Tantillo and his students are using modern computational chemistry methods to explore new principles governing chemical reactivity. The principles uncovered transform how organic chemists predict mechanisms and product distributions for many reactions that lead to complex molecules. In addition to the fundamental importance of the mechanistic models uncovered through this research, the project is used to train students from diverse backgrounds in multidisciplinary approaches to mechanistic chemistry and expose them to careers that employ such techniques. In addition, new methods for making applied computational chemistry accessible to blind and visually impaired students are being developed as part of an effort to encourage this group to pursue careers in STEM fields. The results of this research are disseminated, in part, via an outreach program in partnership with a local arboretum.This research advances knowledge in mechanistic organic chemistry through the construction of detailed mechanistic models for carbocation reactivity. In particular, unusual potential energy surfaces for carbocation rearrangements are characterized, non-statistical dynamic effects on carbocation behavior are analyzed and predicted, and models of reactivity are pushed through to the design and testing of new reactions. The specific goals of this project are: (1) To elucidate general principles for controlling the dynamical behavior of species involved in concerted reactions with multiple asynchronous events (2) To design a reaction with a post-transition state bifurcation and predict its product distribution ahead of laboratory experiments. (3) To develop the theozyme dynamics approach into a tool for understanding and designing catalysts that make use of relatively weak noncovalent interactions.