Volume 238, 2022

Predicting third-body collision efficiencies for water and other polyatomic baths

Abstract

Low-pressure-limit microcanonical (collisional activation) and thermal rate constants are predicted using a combination of automated ab initio potential energy surface construction, classical trajectories, transition state theory, and a detailed energy- and angular-momentum-resolved collision kernel. Several systems are considered, including CH4 (+M) and HO2 (+M), with an emphasis on systems where experimental information is available for comparison. The a priori approach involves no adjustable parameters, and we show that the predicted thermal rate constants are in excellent agreement with experiments, with average deviations of less than 25%. Notably, the a priori approach is shown to perform equally well for atomic, diatomic, and polyatomic baths, including M = H2O, CO2, and “fuel” baths like M = CH4 and NH3. Finally, the utility of microcanonical rate constants for interpreting trends and inferring mechanistic details in the thermal kinetics is demonstrated.

Graphical abstract: Predicting third-body collision efficiencies for water and other polyatomic baths

Associated articles

Article information

Article type
Paper
Submitted
09 2月 2022
Accepted
11 3月 2022
First published
24 3月 2022

Faraday Discuss., 2022,238, 68-86

Author version available

Predicting third-body collision efficiencies for water and other polyatomic baths

Ahren W. Jasper, Faraday Discuss., 2022, 238, 68 DOI: 10.1039/D2FD00038E

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