Theoretical Spectroscopic Characterization at Low Temperatures of Dimethyl Sulfoxide: The Role of Anharmonicity

The Journal of Physical Chemistry. a
M L SenentD Sadovskii

Abstract

The structural and spectroscopic parameters of dimethyl sulfoxide (DMSO) are predicted from CCSD(T)-F12 calculations that can help to resolve the outstanding problem of the rovibrational spectroscopy. DMSO is a near oblate top that presents a trigonal pyramidal geometry. Rotational parameters are determined at the equilibrium and in selected vibrational states. For the ground state, the rotational constants were calculated to be A0 = 7031.7237 MHz, B0 = 6920.1221 MHz, and C0 = 4223.3389 MHz, at few megahertz from the previous experimental measurements. Ab initio calculations allow us to assert that DMSO rotational constants are strongly dependent on anharmonic effects. Asymmetry increases with the vibrational energy. Harmonic frequencies, torsional parameters, and a two-dimensional potential energy surface (2D-PES) focused to describe the internal rotation of the two methyl groups are determined at the CCSD(T)-F12 level of theory. For the medium and small amplitude motions, anharmonic effects are estimated with MP2 theory getting an excellent agreement with experimental data for the ν11 and ν23 fundamentals. Torsional energies and transitions are computed variationally form the 2D-PES that denotes strong interactions between bo...Continue Reading

References

Dec 16, 1998·Journal of Molecular Spectroscopy·M L Senent
Jan 14, 2003·Environmental Science & Technology·Cecilia ArseneIulia V Patroescu-Klotz
Jan 11, 2005·The Journal of Chemical Physics·Vincenzo Barone
May 5, 2007·The Journal of Chemical Physics·Hans-Joachim WernerFrederick R Manby
Mar 5, 2008·The Journal of Chemical Physics·Kirk A PetersonHans-Joachim Werner
Dec 3, 2008·The Journal of Chemical Physics·Kazim E Yousaf, Kirk A Peterson
Feb 12, 2009·The Journal of Chemical Physics·Gerald KniziaHans-Joachim Werner

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Citations

Nov 29, 2016·Physical Chemistry Chemical Physics : PCCP·A ZanchetA García-Vela
Sep 13, 2019·Physical Chemistry Chemical Physics : PCCP·John W NimanVitaly V Kresin
May 24, 2019·The Journal of Chemical Physics·O YazidiM Mogren Al-Mogren
Oct 22, 2019·Physical Chemistry Chemical Physics : PCCP·Boutheïna KerkeniNicole Feautrier
Mar 13, 2018·The Journal of Physical Chemistry. a·Roman A MotiyenkoJean-Claude Guillemin

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