Quantum theory of molecular collisions in a magnetic field: Efficient calculations based on the total angular momentum representation

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 wave function 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 He-3 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. (C) 2010 American Institute of Physics. [doi:10.1063/1.3503500]