Structure, stability, and properties of the trans peroxo nitrate radical: the importance of nondynamic correlation

TitleStructure, stability, and properties of the trans peroxo nitrate radical: the importance of nondynamic correlation
Publication TypeJournal Article
Year of Publication2014
AuthorsDutta, AKumar, Dar, M, Vaval, N, Pal, S
JournalJournal of Physical Chemistry A
Volume118
Issue8
Pagination1350-1362
Date PublishedFEB
Type of ArticleArticle
ISSN1089-5639
Abstract

We report a comparative single-reference and multireference coupled-cluster investigation on the structure, potential energy surface, and IR spectroscopic properties of the trans peroxo nitrate radical, one of the key intermediates in stratospheric NOx chemistry. The previous single-reference ab initio studies predicted an unbound structure for the trans peroxo nitrate radical. However, our Fock space multireference coupled-cluster calculation confirms a bound structure for the trans peroxo nitrate radical, in accordance with the experimental results reported earlier. Further, the analysis of the potential energy surface in FSMRCC method indicates a well-behaved minima, contrary to the shallow minima predicted by the single-reference coupled-cluster method. The harmonic force field analysis, of various possible isomers of peroxo nitrate also reveals that only the trans structure leads to the experimentally observed IR peak at 1840 cm(-1). The present study highlights the critical importance of nondynamic correlation in predicting the structure and properties of high-energy stratospheric NOx radicals.

DOI10.1021/jp409218c
Type of Journal (Indian or Foreign)Foreign
Impact Factor (IF)2.98
Divison category: 
Physical and Materials Chemistry