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) + Ha → 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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry