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Title: Importance of geometric phase effects in ultracold chemistry

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [2];  [1]
  1. Univ. of Nevada, Las Vegas, NV (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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Here, it is demonstrated that the inclusion of the geometric phase has an important effect on ultracold chemical reaction rates. The effect appears in rotationally and vibrationally resolved integral cross sections as well as cross sections summed over all product quantum states. The effect arises from interference between scattering amplitudes of two reaction pathways: a direct path and a looping path that encircle the conical intersection between the two lowest adiabatic electronic potential energy surfaces. It is magnified when the two scattering amplitudes have comparable magnitude and they scatter into the same angular region which occurs in the isotropic scattering characteristic of the ultracold regime (s-wave scattering). Results are presented for the O + OH → H + O2 reaction for total angular momentum quantum number J = 0–5. Large geometric phase effects occur for collision energies below 0.1 K, but the effect vanishes at higher energies when contributions from different partial waves are included. It is also qualitatively demonstrated that the geometric phase effect can be modulated by applying an external electric field allowing the possibility of quantum control of chemical reactions in the ultracold regime. In this case, the geometric phase plays the role of a “quantum switch” which can turn the reaction “on” or “off”.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1329880
Report Number(s):
LA-UR-15-25024
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 119, Issue 50; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

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Universality and chaoticity in ultracold K+KRb chemical reactions journal July 2017
Non-adiabatic quantum reactive scattering in hyperspherical coordinates journal January 2018

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
inorganic and physical chemistry
ultracold chemistry
geometric phase
chemical reaction dynamics