子动力学.pptVIP

1 An Introduction to Ab Initio Molecular Dynamics Outline: What is ab initio molecular dynamics? What can be done by ab initio molecular dynamics? 一、MD法原理 将微观粒子视为经典粒子，服从 Newton 第二定律 二、MD法基本假定 作用势常见函数表达形式为 大写字母为经验常数 二维周期性边界条件示意图 8 个近邻重复单元包围着中心原胞，为其提供合理的边界条件近似 三维周期边界实例—苏氨酸水溶液模拟 1?1?1nm 的立方原胞含 1 个苏氨酸 ( threonine ) 分子和 24 个水分子 Periodic Boundary Conditions (1?,2?,4?)-4-(1,1-e二甲乙基)-2-烃基环戊羰基酰胺晶体 实验测定与 MD 模拟结果的比较 W. Linert, and F. Renz, J. Chem. Inf. Comput. Sci., 33, 776(1993) GnRH ( gonadotrophin-releaing hormon, 促性腺释放激素 ) 分子构象理论预测 D.G. Hangauer, in Computer Aided Drug Design, T.J. Perun C.L. Propst ed., Marcel Dekker Inc., New York, p253, 1989. MD预测的顺磁性和反磁性冰晶体结构 O.A Karim A.D.J. Haymet, J.Chem. Phys., 89, 6889(1988)) MD法模拟的熔盐体系 T *~V * 相图 D.A. Young B.J. Alder, J. Chem. Phys., 73, 2434(1980) Ru-Al 合金断裂过程动态模拟 C.S. Becquart , D. Kim, J.A, Rifkin, and P.C.Clapp, Mat. Sci. Engin., A170, 87(1993) 经典模型的局限 — 未涉及化学行为的物理本质 化合物的性质 ? 电子结构 化学反应 ? 核与电子运动状态的变化 伴随有电子跃迁、转移、变价的过程，经典的分子模拟不能处理 一、量子力学第一原理 — 多体Shr?dinger方程 物理模型： 分子中电子和原子核均在运动中 粒子间存在着相互作用 二、物理模型的三个基本近似 ⒈ 非相对论近似：? i = ? 0 ⒉ Born-Oppenheimer 近似： 电子与核运动分离 颁奖公告称：The development did not really started until the beginning of the 1960s, when two events became decisive: John Pople’s Contributions John Pople has developed quantum chemistry into a tool that can be used by the general chemist and has thereby brought chemistry into a new era where experiment and theory can work together in the exploration of the properties of molecular systems. Chemistry is no longer a purely experimental science. Pople 最杰出的贡献是 Gaussian 程序 颁奖文件称: The creation, constant improvement, and the extension of the functionality of GAUSSIAN is an outstanding achievement. It is the example for the success of the field and its impact on chemistry and neighboring fields like physics, astrophysics, biochemistry, material sciences, etc. GAUSSIAN is today used by thousands of scientists all over the world . Walter Kohn’s Contributions Walter Kohn’s th