ch3_分子动力学模拟基础.pdf

生物分子模拟与计算 第三章分子动力学模拟基础 主讲教师：卢本卓 计算数学与科学工程计算研究所 一，遍历假设（Ergodic hypothesis ） 时间平均与系综平均 • Values such as pressure or heat capacity generally depend upon the positions and momenta of the N particles that comprise the system. The instantaneous value of the property A can thus be written as : A (p t( ),r N t( )) N • Average value of the property A can be calculated using integral approach: 1  AA p ( limt (r ), tN dt( )) N ave    t 0 时间平均与系综平均 For macroscopic numbers of atoms or molecules (of the order of 1023, Avogadros number is 6 ×1023 ) it is not feasible to determine an initial configuration of the system, and to later integrate equation of the motion which describe its temporal evolution. Boltzmann and Gibbs developed statistical mechanics 。 N N N N N N A dp dr A p r p (r , ) ( , )   遍历性假设：一个分子系统的足够长时间的演化（保持能量守恒）可遍历（或无 限接近）任何微观状态。 A system of molecules will assume, in the long run, all conceivable micro-states that are compatible with the conservation of energy. 时间平均与系综平均 A single system evolving in time is replaced by a large number of replications of the same system that are considered simultaneously. An average quantity measured over long enough time will approach the ensemble average： t t  1 0 1 1