MRD-CI study of the photodissociative behavior of HOOOCl, a molecule relevant to atmospheric chemistry.
Equilibrium geometries have been optimized and harmonic vibrational frequencies calculated for HOOOCl using quadratic configuration interaction and coupled-cluster methods with Dunning's correlation-consistent basis sets. There are two conformers of HOOOCl (a cis and a trans structure) that are very close in energy and separated by a barrier of 3.28 kcal mol(-1). In experiments, these two forms may co-exist. Rotational constants that can be used to experimentally characterize and identify HOOOCl are presented. The electronic absorption spectrum for trans-HOOOCl is calculated using multi-reference configuration interaction methods in order to support the spectroscopic search. At 5.84 eV a remarkably strong transition is computed corresponding to a sigma(Cl-O') --> sigma*(Cl-O')-excitation. In addition, possible photodissociation pathways along the Cl-O' and O'-O bonds for trans-HOOOCl have been examined. Potential photochemistry of HOOOCl is suggested for the first time.
Schnell
Melanie
M
Universität Hannover, Institut für Physikalische Chemie und Elektrochemie, Lehrgebiet A, Callinstrasse 3-3a, D-30167 Hannover, Germany. schnell@pci.uni-hannover.de
Francisco
Joseph S
JS
Peyerimhoff
Sigrid D
SD
D001272:Atmosphere; D002627:Chemistry, Physical / Q000379:methods*; D002713:Chlorine / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D010126:Ozone; D010777:Photochemistry / Q000379:methods*; D012984:Software; D013053:Spectrophotometry / Q000379:methods
D002713:Chlorine; D010126:Ozone; D006859:Hydrogen; D010100:Oxygen