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Title: Density functional characterization of [HClO{sub 2}] potential energy surface

Abstract

The potential energy surface (PES) of [HClO{sub 2}] system has been investigated at second-order Moller-Plesset perturbation (MP2) and density functional theory levels using, respectively, the 6-311++G** and 6-311++G(2df,2pd) basis sets. The structural parameters of the isomers of [HClO{sub 2}] were also optimized at complete active space [CAS(12,12)] self-consistent field level using the 6-31G** basis set. Three isomers of relative thermodynamic stability, HOOCl (1) > HOClO (2) > HClO{sub 2} (3), have been identified as energy minima. Besides these covalently bound minima, various loose hydrogen-bonded complexes (OOH{hor{underscore}ellipsis}Cl 5a(s), 5{prime}a(t), and O{hor{underscore}ellipsis}HOCl 7a(t)) have been located on the singlet and triplet PES. Isomerization, molecular elimination, and direct hydrogen abstraction saddle points have been traced and a qualitative understanding of the mechanism and kinetics of the stratospherically important HO + ClO and HO{sub 2} + Cl reactions has been derived.

Authors:
;
Publication Date:
Research Org.:
Univ. Bonn (DE)
OSTI Identifier:
20000071
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 37; Other Information: PBD: 16 Sep 1999; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; ATMOSPHERIC CHEMISTRY; POTENTIAL ENERGY; SURFACES; RADICALS; CHEMICAL REACTIONS; CHLOROUS ACID; HYDROXIDES; KINETICS

Citation Formats

Sumathi, R., and Peyerimhoff, S.D. Density functional characterization of [HClO{sub 2}] potential energy surface. United States: N. p., 1999. Web. doi:10.1021/jp991390i.
Sumathi, R., & Peyerimhoff, S.D. Density functional characterization of [HClO{sub 2}] potential energy surface. United States. doi:10.1021/jp991390i.
Sumathi, R., and Peyerimhoff, S.D. Thu . "Density functional characterization of [HClO{sub 2}] potential energy surface". United States. doi:10.1021/jp991390i.
@article{osti_20000071,
title = {Density functional characterization of [HClO{sub 2}] potential energy surface},
author = {Sumathi, R. and Peyerimhoff, S.D.},
abstractNote = {The potential energy surface (PES) of [HClO{sub 2}] system has been investigated at second-order Moller-Plesset perturbation (MP2) and density functional theory levels using, respectively, the 6-311++G** and 6-311++G(2df,2pd) basis sets. The structural parameters of the isomers of [HClO{sub 2}] were also optimized at complete active space [CAS(12,12)] self-consistent field level using the 6-31G** basis set. Three isomers of relative thermodynamic stability, HOOCl (1) > HOClO (2) > HClO{sub 2} (3), have been identified as energy minima. Besides these covalently bound minima, various loose hydrogen-bonded complexes (OOH{hor{underscore}ellipsis}Cl 5a(s), 5{prime}a(t), and O{hor{underscore}ellipsis}HOCl 7a(t)) have been located on the singlet and triplet PES. Isomerization, molecular elimination, and direct hydrogen abstraction saddle points have been traced and a qualitative understanding of the mechanism and kinetics of the stratospherically important HO + ClO and HO{sub 2} + Cl reactions has been derived.},
doi = {10.1021/jp991390i},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 37,
volume = 103,
place = {United States},
year = {1999},
month = {9}
}