Quantum Theory of Molecular Collisions in a Magnetic Field: Efficient Calculations Based on the Total Angular Momentum Representation

Abstract

An efficient method is presented for rigorous quantum calculations of atom-molecule and molecule-molecule collisions in a magnetic field. The method is based on the expansion of the wavefunction of the collision complex in basis functions with well-defined total angular momentum in the body-fixed coordinate frame. We outline the general theory of the method for collisions of diatomic molecules in the \(^{2}\Sigma\) and \(^{3}\Sigma\) electronic states with structureless atoms and with unlike \(^{2}\Sigma\) and \(^{3}\Sigma\) molecules. The cross sections for elastic scattering and Zeeman relaxation in low-temperature collisions of CaH(\(^{2}\Sigma^{+}\)) and NH(\(^{3}\Sigma^{-}\)) molecules with \(^{3}\)He atoms converge quickly with respect to the number of total angular momentum states included in the basis set, leading to a dramatic >10-fold enhancement in computational efficiency compared to the previously used methods [A. Volpi and J. L. Bohn, Phys. Rev. A 65, 052712 (2002); R. V. Krems and A. Dalgarno, J. Chem. Phys. 120, 2296 (2004)]. Our approach is thus well suited for theoretical studies of strongly anisotropic molecular collisions in the presence of external electromagnetic fields.