The IR absorption spectra of CH3F doped Ar, Kr and Xe solutions have been recorded near the melting point. The full widths at half maximum of fundamental bands increase noticeably after crystallization of the Xe and Kr solutions. A slight narrowing of the bands is observed just below the freezing point of the Ar solution. Treated in the framework of the Debye model for the J-diffusion of a symmetric top rotation, the results suggest a weaker perturbation of rotational motion of CH3F in the ordered Xe and Kr solids at least near the freezing point. At the same time, molecular rotation becomes more hindered when going to solid Ar. The broadening effect has been found to correlate with a hopping increase of the vibrational energy relaxation time, measured by the IR-IR double resonance method.
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http://dx.doi.org/10.1016/s1386-1425(00)00240-7 | DOI Listing |
J Mol Model
September 2022
School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban, 4000, South Africa.
A search has been conducted, by means of ab initio molecular orbital theory, for potential tetrel-bonded complexes formed between the fluorinated methanes methyl fluoride, difluoromethane and fluoroform, and the related hydrides ammonia, water, hydrogen fluoride, phosphine, hydrogen sulphide and hydrogen chloride. Eleven such complexes have been identified, six containing CHF and five CHF. The complexes are typically less strongly bound than their hydrogen-bonded counterparts, and the interaction energies vary in a consistent way with the periodic trend of the electron donors.
View Article and Find Full Text PDFSci Data
March 2022
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
High-level ab initio quantum chemical (QC) molecular potential energy surfaces (PESs) are crucial for accurately simulating molecular rotation-vibration spectra. Machine learning (ML) can help alleviate the cost of constructing such PESs, but requires access to the original ab initio PES data, namely potential energies computed on high-density grids of nuclear geometries. In this work, we present a new structured PES database called VIB5, which contains high-quality ab initio data on 5 small polyatomic molecules of astrophysical significance (CHCl, CH, SiH, CHF, and NaOH).
View Article and Find Full Text PDFJ Phys Chem A
July 2019
Laboratorium für Physikalische Chemie , ETH Zürich , Vladimir-Prelog-Weg 2 , CH-8093 Zürich , Switzerland.
We report results on nuclear spin symmetry conservation studied by high resolution spectroscopy of relative line intensities for the A and E nuclear spin isomers of symmetric top molecules CHD, CHD, CHF, and CHCl in supersonic jet expansions with He and Ar as carrier gases. Infrared absorption spectra were measured around 3000 cm by an infrared (lead salt) diode laser and a continuous wave IR-OPO (infrared optical parametric oscillator) locked to a frequency comb. A detailed analysis of the R(2)-line intensities of the CH-stretching fundamental shows that nuclear spin symmetry is conserved for CHD, CHF, and CHCl during the expansion.
View Article and Find Full Text PDFJ Chem Phys
March 2018
Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, 2519 Jiefang Road, Changchun 130023, People's Republic of China.
A first effective six-dimensional ab initio potential energy surface (PES) for CHF-H which explicitly includes the intramolecular Q stretching normal mode of the CHF monomer is presented. The electronic structure computations have been carried out at the explicitly correlated coupled cluster level of theory [CCSD(T)-F12a] with an augmented correlation-consistent triple zeta basis set. Five-dimensional analytical intermolecular PESs for ν(CHF) = 0 and 1 are then obtained by fitting the vibrationally averaged potentials to the Morse/Long-Range (MLR) potential function form.
View Article and Find Full Text PDFPhys Chem Chem Phys
July 2015
Synchrotron SOLEIL, L'Orme des Merisiers, St. Aubin BP 48, 91192 Gif sur Yvette, France.
Utilizing the vacuum ultraviolet (VUV) synchrotron radiation and a double imaging photoelectron photoion coincidence (i(2)PEPICO) technique, we have measured the adiabatic ionization energies (AIEs) of the overlapped A(2)A1 and B(2)E electronic states of CH3Cl(+) and CH3F(+) ions. We show that the two overlapped electronic states can be separated in the electron and ion kinetic energy correlation diagrams based on their state-specific dissociation dynamics, leading to different kinetic energies released in dissociation, along the CH3(+) fragmentation channel. Thus the correlation diagrams yielded values of 13.
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