Wu Yinghua, Batista Victor S
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
J Chem Phys. 2006 Jun 14;124(22):224305. doi: 10.1063/1.2202847.
The excited-state intramolecular proton-transfer dynamics associated with the keto-enolic tautomerization reaction in 2-(2(')-hydroxyphenyl)-oxazole is simulated according to a numerically exact quantum-dynamics propagation method and a full-dimensional excited-state potential energy surface, based on an ab initio reaction surface Hamiltonian. The reported simulations involve the propagation of 35-dimensional wave packets according to the recently developed matching-pursuit/split-operator-Fourier-transform (MP/SOFT) method by Wu and Batista. The underlying propagation scheme recursively applies the time-evolution operator as defined by the Trotter expansion to second order accuracy in dynamically adaptive coherent-state expansions. Computations of time-dependent survival amplitudes, photoabsorption cross sections, and time-dependent reactant(product) populations are compared to the corresponding calculations based on semiclassical approaches, including the Herman-Kluk semiclassical initial value representation method. The reported results demonstrate the capabilities of the MP/SOFT method as a valuble computational tool to study ultrafast reaction dynamics in polyatomic systems as well as to validate semiclassical simulations of complex (nonintegrable) quantum dynamics in multidimensional model systems.
基于从头算反应表面哈密顿量，根据数值精确的量子动力学传播方法和全维激发态势能面，模拟了2-(2(')-羟基苯基)-恶唑中与酮-烯醇互变异构反应相关的激发态分子内质子转移动力学。所报道的模拟涉及根据Wu和Batista最近开发的匹配追踪/分裂算符-傅里叶变换（MP/SOFT）方法传播35维波包。潜在的传播方案在动态自适应相干态展开中，将由Trotter展开定义的时间演化算符递归应用到二阶精度。将时间相关的存活振幅、光吸收截面以及时间相关的反应物（产物）布居数的计算结果与基于半经典方法的相应计算结果进行比较，包括Herman-Kluk半经典初值表示方法。所报道的结果证明了MP/SOFT方法作为一种有价值的计算工具，可用于研究多原子系统中的超快反应动力学，以及验证多维模型系统中复杂（不可积）量子动力学的半经典模拟。
