Nonrigidity effects -- a missing puzzle piece in the description of low-energy anisotropic molecular collisions
arXiv:1907.05130 · doi:10.1021/acs.jctc.0c00183
Abstract
Cold collisions serve as a very sensitive probe of the interaction potential. In the recent study of Klein et al. (Nature Phys. 13, 35-38 (2017)) the one-parameter scaling of the interaction potential was necessary to obtain agreement between theoretical and observed patterns of the orbiting resonances for excited metastable helium atoms colliding with hydrogen molecules. Here we show that the effect of nonrigidity of the H molecule on the resonant structure, absent in the previous study, is critical to predict correct positions of the resonances in that case. We have complemented the theoretical description of the interaction potential and revised reaction rate coefficients by proper inclusion of the flexibility of the molecule. The calculated reaction rate coefficients are in remarkable agreement with the experimental data without empirical adjustment of the interaction potential. We have shown that even state-of-the-art calculations of the interaction energy cannot ensure agreement with the experiment if such an important physical effect as flexibility of the interacting molecule is neglected. Our findings about the significance of the nonrigidity effects can be especially crucial in cold chemistry, where the quantum nature of molecules is pronounced.
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