A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H2 O. Denis-Alpizar, Y. N. Kalugina, T. Stoecklin [et.al.]
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ArticleSubject(s): синильная кислота | цианистый водород | поверхности потенциальной энергии | столкновения молекул | водородGenre/Form: статьи в журналах Online resources: Click here to access online
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Journal of chemical physics Vol. 139, № 22. P. 224301-1-224301-8Abstract: We present a new four-dimensional potential energy surface for the collisional excitation of HCN
by H2. Ab initio calculations of the HCN–H2 van der Waals complex, considering both molecules
as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double,
and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlationconsistent
triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN–H2 with the nitrogen
pointing towards H2 at an intermolecular separation of 7.20 a0. The corresponding well depth is
−195.20 cm−1. A secondary minimum of −183.59 cm−1 was found for a T-shape configuration with
the H of HCN pointing to the center of mass of H2. We also determine the rovibrational energy levels
of the HCN–para-H2 and HCN–ortho-H2 complexes. The calculated dissociation energies for the
para and ortho complexes are 37.79 cm−1 and 60.26 cm−1, respectively. The calculated ro-vibrational
transitions in the HCN–H2 complex are found to agree by more than 0.5% with the available experimental
data, confirming the accuracy of the potential energy surface.
Библиогр.: 49 назв.
We present a new four-dimensional potential energy surface for the collisional excitation of HCN
by H2. Ab initio calculations of the HCN–H2 van der Waals complex, considering both molecules
as rigid rotors, were carried out at the explicitly correlated coupled cluster with single, double,
and perturbative triple excitations [CCSD(T)-F12a] level of theory using an augmented correlationconsistent
triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN–H2 with the nitrogen
pointing towards H2 at an intermolecular separation of 7.20 a0. The corresponding well depth is
−195.20 cm−1. A secondary minimum of −183.59 cm−1 was found for a T-shape configuration with
the H of HCN pointing to the center of mass of H2. We also determine the rovibrational energy levels
of the HCN–para-H2 and HCN–ortho-H2 complexes. The calculated dissociation energies for the
para and ortho complexes are 37.79 cm−1 and 60.26 cm−1, respectively. The calculated ro-vibrational
transitions in the HCN–H2 complex are found to agree by more than 0.5% with the available experimental
data, confirming the accuracy of the potential energy surface.
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