Symmetry breaking: a classic example of quantum interference captured by mixed quantum/classical theory

Journal article

The phenomena of propensity and inverse propensity are explored using time-dependent mixed quantum classical theory, MQCT, in which the rotational motion of the molecule is treated quantum mechanically, whereas the scattering process is described classically. Good agreement with the results of accurate full-quantum calculations is reported for a closed shell approximation to the NO + Ar system. It is shown that MQCT reproduces both phenomena in a broad range of the final states of the molecule and for various initial rotational states, offering a unique time-dependent insight. It permits seeing that both propensity and inverse propensity occur due to efficient depopulation of some states at the early postcollisional stage of the scattering process, when the molecule exists in a coherent superposition of many excited states that span a very broad range of angular momentum quantum numbers, populated by an efficient stepladder process of many consecutive transitions with small Δj.

Authors: Imanzi, K; Bostan, D; McCrea, M; Featherstone, J; Brouard, M

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: American Chemical Society
• Journal: Journal of Physical Chemistry Letters
• Volume: 14
• Issue: 47
• Pages: 10617-10623
• Publication date: 2023-11-20
• Acceptance date: 2023-11-17
• DOI: 10.1021/acs.jpclett.3c02887
• EISSN: 1948-7185
• Pmid: 37982682
• Language: English
• Keywords: computational chemistry; energy levels; molecules; phase transitions; FFR; collisions