Determination of the structures of benzotriazole(H2O)(1,2) clusters by IR-UV spectroscopy and ab initio theory

Citation
M. Schmitt et al., Determination of the structures of benzotriazole(H2O)(1,2) clusters by IR-UV spectroscopy and ab initio theory, PHYS CHEM P, 3(19), 2001, pp. 4218-4227
Citations number
23
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN journal
1463-9076 → ACNP
Volume
3
Issue
19
Year of publication
2001
Pages
4218 - 4227
Database
ISI
SICI code
1463-9076(2001)3:19<4218:DOTSOB>2.0.ZU;2-I
Abstract
The structures of benzotriazole monomer and clusters have been examined by benzotriazole(H2O)(1,2) comparison of R2PI spectra and IR-UV double resonan ce spectra with the results of ab initio based normal mode calculations. Th e structures of the binary benzotriazole-water cluster and the n = 2 cluste r are shown to be cyclic. Based on these cyclic structures the intermolecul ar vibronic transitions have been assigned by comparison with ab initio nor mal mode analysis. The cyclic clusters can be viewed as a benzotriazole(H2O )(1,2) precursor to a transition state for H-atom transfer from the 1- to t he 2-position in benzotriazole. The activation energy for this tautomerism has been calculated for the monomer and the n = 1 and 2 cluster as the diff erence between the stabilization energy of the more stable tautomer and the respective transition state. It has been found to decrease rapidly, with i ncreasing cluster size.