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An improved coupled-states approximation including the nearest neighbor Coriolis couplings for diatom-diatom
Dongzheng Yang1, Xixi Hu1, Dong H Zhang2
1Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Abstract:
Solving the time-independent close coupling equations of a diatom-diatom inelastic collision system by using the rigorous close-coupling approach is numerically difficult because of its expensive matrix manipulation. The coupled-states approximation decouples the centrifugal matrix by neglecting the important Coriolis couplings completely. In this work, a new approximation method based on the coupled-states approximation is presented and applied to time-independent quantum dynamic calculations. This approach only considers the most important Coriolis coupling with the nearest neighbors and ignores weaker Coriolis couplings with farther K channels. As a result, it reduces the computational costs without a significant loss of accuracy. Numerical tests for para-H2+ortho-H2 and para-H2+HD inelastic collision were carried out and the results showed that the improved method dramatically reduces the errors due to the neglect of the Coriolis couplings in the coupled-states approximation. This strategy should be useful in quantum dynamics of other systems.
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