Thermal rate constants for the O(3P) + HBr and O(3P) + DBr reactions: Transition-state theory and quantum mechanical calculations

Antonio G.S. De Oliveira-Filho, Fernando R. Ornellas, Kirk A. Peterson, Steven L Mielke

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

The O(3P) + HBr → OH + Br and O(3P) + DBr → OD + Br reactions are studied on a recent high-quality ab initio-based potential energy surface. Thermal rate constants over the 200-1000 K temperature range, calculated using variational transition-state theory (VTST) with the small-curvature tunneling (SCT) correction and quantum mechanical methods with the J-shifting approximation (QM/JS) for zero total angular momentum (J = 0), are reported. These results are compared to the available experimental data, which lie in the ranges of 221-554 and 295-419 K for O + HBr and O + DBr, respectively. The rate constants, in cm3 molecule-1 s -1 and at 298 K, for the O + HBr reaction are 3.66 × 10 -14 for VTST, 3.80 × 10-14 for QM/JS, and 3.66 × 10-14 for the average of eight experimental measurements.

Original languageEnglish (US)
Pages (from-to)12703-12710
Number of pages8
JournalJournal of Physical Chemistry A
Volume117
Issue number48
DOIs
StatePublished - Dec 5 2013

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