NOx Catalyzed Pathway of Stratospheric Ozone Depletion: A Coupled Cluster Investigation

• Published in: Journal of chemical theory and computation 2012-06, Vol.8 (6), p.1895-1901
• Main Authors: Dutta, Achintya Kumar, Vaval, Nayana, Pal, Sourav
• Format: Article
• Language: English
• ISSN: 1549-9618
• DOI: 10.1021/ct300209s

We report a theoretical investigation on the NOx catalyzed pathways of stratospheric ozone depletion using highly accurate coupled cluster methods. These catalytic reactions represent a great challenge to state-of-the-art ab initio methods, while their mechanisms remain unclear to both experimentalists and theoreticians. In this work, we have used the so-called "gold standard of quantum chemistry," the CCSD(T) method, to identify the saddle points on NOx-based reaction pathways of ozone hole formation. Energies of the saddle points are calculated using the multireference variants of coupled cluster methods. The calculated activation energies and rate constants show good agreement with available experimental results. Tropospheric precursors to stratospheric NOx radicals have been identified, and their potential importance in stratospheric chemistry has been discussed. Our calculations resolve previous conflicts between ab initio and experimental results for a trans nitro peroxide intermediate, in the NOx catalyzed pathway of ozone depletion.