An Accurate Ab Initio HOCl Potential Energy Surface, Vibrational and Rotational Calculations, and Comparison with Experiment

Skokov, Sergei; Peterson, Kirk A.; Bowman, Joel M.

doi:10.1063/1.476865

An Accurate Ab Initio HOCl Potential Energy Surface, Vibrational and Rotational Calculations, and Comparison with Experiment

Journal Article · Sat Aug 15 00:00:00 EDT 1998 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.476865· OSTI ID:1700516

Skokov, Sergei ^[1]; Peterson, Kirk A. ^[2]; Bowman, Joel M. ^[1]

Emory University
BATTELLE (PACIFIC NW LAB)

Accurate ab initio multireference configuration interaction (CI) calculations with large correlation-consistent basis sets are performed for HOCl. After extrapolation to the complete basis set limit, the ab initio data are precisely fit to give a semiglobal three-dimensional potential energy surface to describe HOCl?Cl+OH from high overtone excitation of the OH-stretch. The average absolute deviation between the ab initio and fitted energies is 4.2?cm-1 for energies up to 60 kcal/mol relative to the HOCl minimum. Vibrational energies of HOCl including the six overtones of the OH-stretch are computed using a vibrational-Cl method on the fitted potential and also on a slightly adjusted potential. Near-spectroscopic accuracy is obtained using the adjusted potential; the average absolute deviation between theory and experiment for 19 experimentally reported states is 4.8?cm-1. Very good agreement with experiment is also obtained for numerous rotational energies for the ground vibrational state, the ClO-stretch fundamental, and the fifth overtone of the OH-stretch.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1700516

Report Number(s):: PNWD-SA-4538

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 109

Country of Publication:: United States

Language:: English

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