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Journal of Physical Chemistry A, Vol.101, No.17, 3045-3048, 1997
Tunneling Splittings in Predissociated HF Dimer
We have calculated converged energies and tunneling splittings of the intramolecular stretching fundamentals and high-frequency, low-frequency combination levels of (HF)(2) on three potential energy surfaces. The resonance states are located against a broad background of continuum states by a moment-based stabilization method. The mean unsigned deviation from experiment for six tunneling splittings on the recently proposed S2 surface and on the BJKKL surface of Bunker et al. are 28% and 24%, respectively, as compared to 41% for the previously available results on the SQSBDE surface of Quack and Suhm. The results for the S2 surface are more accurate for excitation of the hydrogen-bond acceptor mode than for the hydrogen-bond donor mode, whereas those for the BJKKL surface are more accurate for the latter than the former.
Keywords:HYDROGEN-FLUORIDE DIMER;QUASI-ADIABATIC CHANNELS;MONTE-CARLO CALCULATIONS;REACTION-PATH ANALYSIS;VIBRATIONAL PREDISSOCIATION;RESONANCE ENERGIES;STABILIZATION CALCULATIONS;(HF)2;DYNAMICS;SPECTRUM