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A high-accuracy theoretical study of the CHnP Systems n = 1–3

Authors

  • Ringo Rey-Villaverde,

    1. Departamento de Química Física, Facultad de Química, Universidad de Vigo, Vigo, Spain
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  • Hubert Cybulski,

    1. Center for Research in Biological Chemistry and Molecular Materials (CIQUS), University of Santiago de Compostela, Santiago, Spain
    2. Department of Physics, Astronomy and Informatics, Institute of Physics, Nicolaus Copernicus University, Torun, Poland
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  • Jesús R. Flores,

    Corresponding author
    • Departamento de Química Física, Facultad de Química, Universidad de Vigo, Vigo, Spain
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  • Berta Fernández

    1. Center for Research in Biological Chemistry and Molecular Materials (CIQUS), University of Santiago de Compostela, Santiago, Spain
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  • For PH3 the webbook value was used; that of the tables is 5.4 ±1.7 kJ/mol.

E-mail: flores@uvigo.es

Abstract

We have performed high-level electronic structure computations on the most important species of the CHnP systems n = 1–3 to characterize them and provide reliable information about the equilibrium and vibrationally averaged molecular structures, rotational constants, vibrational frequencies (harmonic and anharmonic), formation enthalpies, and vertical excitation energies. Those chemical systems are intermediates for several important reactions and also prototypical phosphorus-carbon compounds; however, they are often elusive to experimental detection. The present results significantly complement their knowledge and can be used as an assessment of the experimental information when available. The explicitly correlated coupled-cluster RCCSD(T)-F12 method has been used for geometry optimizations and vibrational frequency calculations. Vibrational configuration interaction theory has been used to account for anharmonicity effects. Basis-set limit extrapolations have been carried out to determine accurate thermochemical quantities. Electronic excited states have been calculated with coupled-cluster approaches and also by means of the multireference configuration interaction method. © 2013 Wiley Periodicals, Inc.

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