Journal article
Rovibrational eigenenergy structure of the [H,C,N] molecular system
Authors list: Mellau, Georg Ch.
Publication year: 2011
Journal: The Journal of Chemical Physics
Volume number: 134
Issue number: 19
ISSN: 0021-9606
Open access status: Bronze
DOI Link: https://doi.org/10.1063/1.3590026
Publisher: American Institute of Physics
Abstract:
The vibrational-rotational eigenenergy structure of the [H,N,C] molecular system is one of the key features needed for a quantum mechanical understanding of the HCN reversible arrow HNC model reaction. The rotationless vibrational structure corresponding to the multidimensional double well potential energy surface is well established. The rotational structure of the bending vibrational states up to the isomerisation barrier is still unknown. In this work the structure of the rotational states for low and high vibrational angular momentum is described from the ground state up to the isomerisation barrier using hot gas molecular high resolution spectroscopy and rotationally assigned ab initio rovibronic states. For low vibrational angular momentum the rotational structure of the bending excitations splits in three regions. For J < 40 the structure corresponds to that of a typical linear molecule, for 40 < J < 60 has an approximate double degenerate structure and for J > 60 the splitting of the e and f components begins to decrease and the rotational constant increases. For states with high angular momentum, the rotational structure evolves into a limiting structure for v(2) > 7 -the molecule is locked to the molecular axis. For states with v(2) > 11 the rotational structure already begins to accommodate to the lower rotational constants of the isomerisation states. The vibrational energy begins to accommodate to the levels above the barrier only at high vibrational excitations of v(2) > 22 just above the barrier whereas this work shows that the rotational structure is much more sensitive to the double well structure of the potential energy surface. The rotational structure already experiences the influence of the barrier at much lower energies than the vibrational one. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3590026]
Citation Styles
Harvard Citation style: Mellau, G. (2011) Rovibrational eigenenergy structure of the [H,C,N] molecular system, The Journal of Chemical Physics, 134(19), Article 194302. https://doi.org/10.1063/1.3590026
APA Citation style: Mellau, G. (2011). Rovibrational eigenenergy structure of the [H,C,N] molecular system. The Journal of Chemical Physics. 134(19), Article 194302. https://doi.org/10.1063/1.3590026
Keywords
010 STATES; BAND SYSTEM; BENDING VIBRATIONAL LADDER; (D2O)-O-16; DIPOLE; GAS EMISSION-SPECTROSCOPY; HCN; HNC
