Structural and Dynamic Properties of a Hydrogen Bond from the Study of the CH3Cl–HCl Complex and Isotopic Species

The microwave (4–20 GHz range) and infrared (HCl and DCl stretch ranges) spectra of six isotopic species of the CH3Cl–HCl hydrogen bond complex have been recorded for the first time and analyzed with the support of high level ab initio calculations (MP2 and CCSD(T) levels). Accurate molecular parame...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-11, Vol.117 (47), p.12569-12580
Main Authors: Goubet, Manuel, Asselin, Pierre, Soulard, Pascale, Madebène, Bruno
Format: Article
Language:English
Subjects:
Ab initio calculations
Atomic and molecular physics
Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations)
Chemical Physics
Chemical Sciences
Coupled cluster theory
Deuterium - chemistry
Electronic structure of atoms, molecules and their ions: theory
Exact sciences and technology
Hydrochloric Acid - chemistry
Hydrogen Bonding
Methyl Chloride - chemistry
Molecular Structure
or physical chemistry
Physics
Quantum Theory
Spectroscopy, Fourier Transform Infrared
Theoretical and
Thermodynamics
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Summary:The microwave (4–20 GHz range) and infrared (HCl and DCl stretch ranges) spectra of six isotopic species of the CH3Cl–HCl hydrogen bond complex have been recorded for the first time and analyzed with the support of high level ab initio calculations (MP2 and CCSD(T) levels). Accurate molecular parameters, including rotational, quartic centrifugal distortion, and nuclear-quadrupole coupling constants, vibrational frequencies, and anharmonic coupling constants, are presented in this paper. These parameters have then been used to estimate the hydrogen bond geometry and confirm the strong coupling between intramolecular and low frequency intermolecular modes. Experimental and theoretical evidence, in agreement with each other, tend to point out a free rotation of the CH3Cl unit in the complex, emphasizing the very peculiar dynamical properties of a hydrogen bond and, consequently, the necessity of taking those effects into account to correctly model the intra- and intermolecular interactions.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp407309a