Quantum mechanical calculation of energy dependence of OCl/OH product branching ratio and product quantum state distributions for the O(1D) + HCl reaction on all three contributing electronic state potential energy surfaces.
OCl/OH product branching ratios are calculated as a function of total energy for the O( (1) D) + HCl reaction using quantum wavepacket methods. The calculations take account of reaction on all the three electronic state potential energy surfaces which correlate with both reactants and products. Our results show that reaction on the excited electronic state surfaces has a large effect on the branching ratio at higher energies and that these surfaces must therefore be fully taken into account. The calculations use the potential energy surfaces of Nanbu and co-workers. Product vibrational and rotational quantum state distributions are also calculated as a function of energy for both product channels. Inclusion of the excited electronic state potential energy surfaces improves the agreement of the predicted product vibrational quantum state distributions with experiment for the OH product channel. For OCl agreement between theory and experiment is retained for the vibrational quantum state distributions when the excited electronic state potential energy surfaces are included in the analysis. For the rotational state distributions good agreement between theory and experiment is maintained for energies at which experimental results are available. At higher energies, above 0.7 eV of total energy, the OCl rotational state distributions predicted using all three electronic state potential energy surfaces shift to markedly smaller rotational quantum numbers.
Yang
Huan
H
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Han
Ke-Li
KL
Nanbu
Shinkoh
S
Nakamura
Hiroki
H
Balint-Kurti
Gabriel G
GG
Zhang
Hong
H
Smith
Sean C
SC
Hankel
Marlies
M
D004583:Electrons; D006851:Hydrochloric Acid / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D006997:Hypochlorous Acid / Q000737:chemistry*; D011789:Quantum Theory; D012399:Rotation; D026082:Singlet Oxygen / Q000737:chemistry*; D013499:Surface Properties; D014732:Vibration
D026082:Singlet Oxygen; D017665:Hydroxyl Radical; D006997:Hypochlorous Acid; D006851:Hydrochloric Acid