skip to main content

SciTech ConnectSciTech Connect

Title: A new ab initio potential energy surface for the collisional excitation of HCN by para- and ortho-H{sub 2}

We present a new four-dimensional potential energy surface for the collisional excitation of HCN by H{sub 2}. Ab initio calculations of the HCN–H{sub 2} 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 correlation-consistent triple zeta (aVTZ) basis set. The equilibrium structure is linear HCN–H{sub 2} with the nitrogen pointing towards H{sub 2} at an intermolecular separation of 7.20 a{sub 0}. The corresponding well depth is −195.20 cm{sup −1}. A secondary minimum of −183.59 cm{sup −1} was found for a T-shape configuration with the H of HCN pointing to the center of mass of H{sub 2}. We also determine the rovibrational energy levels of the HCN–para-H{sub 2} and HCN–ortho-H{sub 2} complexes. The calculated dissociation energies for the para and ortho complexes are 37.79 cm{sup −1} and 60.26 cm{sup −1}, respectively. The calculated ro-vibrational transitions in the HCN–H{sub 2} complex are found to agree by more than 0.5% with the available experimental data, confirming the accuracy of the potential energy surface.
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [3] ;  [2] ;  [5]
  1. Université de Bordeaux, ISM, CNRS UMR 5255, 33405 Talence Cedex (France)
  2. (Cuba)
  3. LOMC - UMR 6294, CNRS-Université du Havre, 25 rue Philippe Lebon, BP 540, 76058, Le Havre (France)
  4. (Russian Federation)
  5. Departamento de Física, Universidad de Matanzas, Matanzas 40100 (Cuba)
Publication Date:
OSTI Identifier:
22253865
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 22; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; DISSOCIATION ENERGY; ENERGY LEVELS; EXCITATION; HYDROCYANIC ACID; HYDROGEN; POTENTIAL ENERGY; SURFACES; VAN DER WAALS FORCES