Structure, spectroscopy, and thermal decomposition of 5-chloro-1,2,3,4-thiatriazole: A He i photoelectron, infrared, and quantum chemical study

T. Pasinszki, Dániel Dzsotján, Gábor Vass, Jean Claude Guillemin

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

5-Chloro-1,2,3,4-thiatriazole has been investigated in the gas phase for the first time by mid-infrared and He I photoelectron spectroscopy. The ground-state geometry has been obtained from quantum chemical calculations at the CCSD(T) and B3LYP levels using aug-cc-pVTZ basis set. Ionization potentials have been determined and the electronic structure has been discussed within the frame of molecular orbital theory. IR and photoelectron spectroscopies, supported by quantum chemical calculations at the B3LYP and SAC-CI levels, provide a detailed investigation into the vibrational and electronic character of the molecule. Thermal stability of 5-chloro-1,2,3,4-thiatriazole has been studied both experimentally and theoretically. Flash vacuum thermolysis of the molecule produces fast quantitatively N2, ClCN, and sulfur. Theoretical calculations at the CCSD(T)//B3LYP level predict competitive decomposition routes, starting either with a retro-cycloaddition reaction leading to N2S and ClCN or with a ring opening to chlorothiocarbonyl azide intermediate, to produce finally N2, S, and ClCN. Calculations also predict that N2S is reactive and decomposes in bimolecular reactions to N2 and S2.

Original languageEnglish
Pages (from-to)1603-1610
Number of pages8
JournalStructural Chemistry
Volume26
Issue number5-6
DOIs
Publication statusPublished - Aug 19 2015

Fingerprint

Photoelectrons
thermal decomposition
photoelectrons
Pyrolysis
Spectroscopy
Infrared radiation
decomposition
Photoelectron spectroscopy
spectroscopy
photoelectron spectroscopy
Thermolysis
Molecules
Azides
Cycloaddition
Ionization potential
cycloaddition
Molecular orbitals
Sulfur
ionization potentials
Ground state

Keywords

  • Ab initio
  • DFT
  • IR
  • Structure
  • Thermolysis
  • UPS

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Structure, spectroscopy, and thermal decomposition of 5-chloro-1,2,3,4-thiatriazole : A He i photoelectron, infrared, and quantum chemical study. / Pasinszki, T.; Dzsotján, Dániel; Vass, Gábor; Guillemin, Jean Claude.

In: Structural Chemistry, Vol. 26, No. 5-6, 19.08.2015, p. 1603-1610.

Research output: Contribution to journalArticle

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