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Title: Quantum-mechanical study of energies, structures, and vibrational spectra of the H(D)Cl complexed with dimethyl ether

Interaction energies, molecular structure and vibrational frequencies of the binary complex formed between H(D)Cl and dimethyl ether have been obtained using quantum-chemical methods. Equilibrium and vibrationally averaged structures, harmonic and anharmonic wavenumbers of the complex and its deuterated isotopomer were calculated using harmonic and anharmonic second-order perturbation theory procedures with Density Functional Theory B3LYP and B2PLYP-D and ab initio Møller-Plesset second-order methods, and a 6-311++G(3d,3p) basis set. A phenomenological model describing anharmonic-type vibrational couplings within hydrogen bonds was developed to explain the unique broadening and fine structure, as well as the isotope effect of the Cl–H and Cl–D stretching IR absorption bands in the gaseous complexes with dimethyl ether, as an effect of hydrogen bond formation. Simulations of the rovibrational structure of the Cl–H and Cl–D stretching bands were performed and the results were compared with experimental spectra.
Authors:
; ; ;  [1]
  1. Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Kraków (Poland)
Publication Date:
OSTI Identifier:
22493270
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 20; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ABSORPTION SPECTROSCOPY; CHEMICAL BONDS; CHLORINE COMPLEXES; COMPARATIVE EVALUATIONS; DENSITY FUNCTIONAL METHOD; EQUILIBRIUM; FINE STRUCTURE; HYDROGEN; INFRARED SPECTRA; METHYL ETHER; MOLECULAR STRUCTURE; PERTURBATION THEORY; QUANTUM MECHANICS