Rassolov Vitaly A, Garashchuk Sophya, Schatz George C
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA.
J Phys Chem A. 2006 Apr 27;110(16):5530-6. doi: 10.1021/jp056741+.
The quantum trajectory approach is generalized to arbitrary coordinate systems, including curvilinear coordinates. This allows one to perform an approximate quantum trajectory propagation, which scales favorably with system size, in the same framework as standard quantum wave packet dynamics. The trajectory formulation is implemented in Jacobi coordinates for a nonrotating triatomic molecule. Wave packet reaction probabilities are computed for the O(3P) + H2 --> OH + H reaction using the approximate quantum potential. The latter is defined by the nonclassical component of the momentum operator expanded in terms of linear and exponential functions. Unlike earlier implementations with linear functions, the introduction of the exponential function provides an accurate description of asymptotic dynamics for this system and gives good agreement of approximate reaction probabilities with accurate quantum calculations.
量子轨迹方法被推广到任意坐标系，包括曲线坐标系。这使得人们能够在与标准量子波包动力学相同的框架内进行近似量子轨迹传播，其随系统大小的缩放情况良好。轨迹公式在非旋转三原子分子的雅可比坐标中实现。使用近似量子势计算了(O(3P)+H_2→OH + H)反应的波包反应概率。后者由动量算符的非经典分量定义，该分量用线性和指数函数展开。与早期使用线性函数的实现不同，指数函数的引入为该系统的渐近动力学提供了准确描述，并使近似反应概率与精确量子计算结果吻合良好。
