Mixed Quantum/Classical Theory for Rotational Energy Exchange in Symmetric-Top-Rotor + Linear-Rotor Collisions and a Case Study of the ND3 + D2 System

Document Type


Publication Date



Royal Society of Chemistry

Source Publication

Physical Chemistry Chemical Physics

Source ISSN


Original Item ID

DOI: 10.1039/d3cp01642k


Manifestation of the quantum interference effect in the oscillation of scattering cross section is explored using the N2 + O system as a case study. Calculations are carried out for two electronic PESs of the system, for various initial rotational states of N2, in a broad range of N2 + O collision energies and using three theoretical methods: two versions of the approximate mixed quantum/classical theory (MQCT and AT-MQCT) and the accurate full-quantum coupled-channel method (implemented in MOLSCAT). A good agreement between different methods is observed, especially at high energies. Elastic scattering cross-sections oscillate as a function of collision energy, which is the result of quantum interference. The effects of initial rotational excitation and of the PES properties are studied in detail. For the final (thermally averaged) cross sections, both MOLSCAT and MQCT calculations predict a rather regular pattern of quantum oscillations that persist through a broad range of collision energies and expand into the low-energy regime where quantum scattering resonances are common. The difference between cross sections predicted by MQCT and MOLSCAT decreases from ∼8% at low energies to ∼2% at high energies. Experimental data available at high collision energies are well reproduced.


Physical Chemistry Chemical Physics, Vol. 26 (2023): 15683-15692. DOI