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 فرؤری 2022
Accepted
11 مارٕچ 2022
First published
24 مارٕچ 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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements