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• W2083692015 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⇌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 v2 > 7 – the molecule is locked to the molecular axis. For states with v2 > 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 v2 > 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." @default.
• W2083692015 created "2016-06-24" @default.
• W2083692015 creator A5062777262 @default.
• W2083692015 date "2011-05-21" @default.
• W2083692015 modified "2023-10-10" @default.
• W2083692015 title "Rovibrational eigenenergy structure of the [H,C,N] molecular system" @default.
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• W2083692015 doi "https://doi.org/10.1063/1.3590026" @default.
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