Vibrational analysis of HOCl up to 98{percent} of the dissociation energy with a Fermi resonance Hamiltonian
- Grenoble High Magnetic Field Laboratory, MPI-FKF and CNRS, BP 166, F-38042 Grenoble Cedex 09 (France)
- Laboratoire de Spectrometrie Physique, CNRS UMR 5588, Universite Joseph Fourier-Grenoble I, BP 87, F-38402 St Martin dHeres Cedex (France)
- Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322 (United States)
We have analyzed the vibrational energies and wave functions of HOCl obtained from previous {ital ab initio} calculations [J. Chem. Phys. {bold 109}, 2662 (1998); {bold 109}, 10273 (1998)]. Up to approximately 13&hthinsp;000 cm{sup {minus}1}, the normal modes are nearly decoupled, so that the analysis is straightforward with a Dunham model. In contrast, above 13&hthinsp;000 cm{sup {minus}1} the Dunham model is no longer valid for the levels with no quanta in the OH stretch (v{sub 1}=0). In addition to v{sub 1}, these levels can only be assigned a so-called polyad quantum number P=2v{sub 2}+v{sub 3}, where 2 and 3 denote, respectively, the bending and OCl stretching normal modes. In contrast, the levels with v{sub 1}{ge}2 remain assignable with three v{sub i} quantum numbers up to the dissociation (D{sub 0}=19&hthinsp;290&hthinsp;cm{sup {minus}1}). The interaction between the bending and the OCl stretch ({omega}{sub 2}{congruent}2{omega}{sub 3}) is well described with a simple, fitted Fermi resonance Hamiltonian. The energies and wave functions of this model Hamiltonian are compared with those obtained from {ital ab initio} calculations, which in turn enables the assignment of many additional {ital ab initio} vibrational levels. Globally, among the 809 bound levels calculated below dissociation, 790 have been assigned, the lowest unassigned level, No. 736, being located at 18&hthinsp;885 cm{sup {minus}1} above the (0,0,0) ground level, that is, at about 98{percent} of D{sub 0}. In addition, 84 {open_quotes}resonances{close_quotes} located above D{sub 0} have also been assigned. Our best Fermi resonance Hamiltonian has 29 parameters fitted with 725 {ital ab initio} levels, the rms deviation being of 5.3 cm{sup {minus}1}. This set of 725 fitted levels includes the full set of levels up to No. 702 at 18&hthinsp;650 cm{sup {minus}1}. The {ital ab initio} levels, which are assigned but not included in the fit, are reasonably predicted by the model Hamiltonian, but with a typical error of the order of 20 cm{sup {minus}1}. The classical analysis of the periodic orbits of this Hamiltonian shows that two bifurcations occur at 13&hthinsp;135 and 14&hthinsp;059 cm{sup {minus}1} for levels with v{sub 1}=0. Above each of these bifurcations two new families of periodic orbits are created. The quantum counterpart of periodic orbits are wave functions with {open_quotes}pearls{close_quotes} aligned along the classical periodic orbits. The complicated sequence of {ital ab initio} wave functions observed within each polyad is nicely reproduced by the wave functions of the Fermi resonance Hamiltonian and by the corresponding shapes of periodic orbits. We also present a comparison between calculated and measured energies and rotational constants for 25 levels, leading to a secure vibrational assignment for these levels. The largest difference between experimental and calculated energies reaches 22 cm{sup {minus}1} close to D{sub 0}. {copyright} {ital 1999 American Institute of Physics.}
- OSTI ID:
- 689943
- Journal Information:
- Journal of Chemical Physics, Vol. 111, Issue 15; Other Information: PBD: Oct 1999
- Country of Publication:
- United States
- Language:
- English
Similar Records
Complex L[sup 2] calculation of the variation of resonance widths of HOCl with total angular momentum
The cavity ringdown spectrum of the visible electronic system of thiophosgene: An estimation of the lifetime of the T[sub 1]([tilde a]; [sup 3]A[sub 2]) triplet state