An improved potential energy surface for the F+H2 reaction |
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| Affiliation: | 1. Department of Chemistry and Biochemistry, University of Colorado, Campus Box 215, Boulder, CO 80309-0215, USA;2. Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USA;1. KeyLaboratory of Advanced Civil Engineering Materials of Ministry of Education, Functional Materials Research Laboratory, School of Materials Science & Engineering, Tongji University, Shanghai 201804, PR China;2. State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Micro-system and Information Technology, Chinese Academy of Sciences, Shanghai 200050, PR China;3. Department of Minging and Materials Engineering, McGill University, Montreal, Quebec, Canada H3A 0C5;1. Departamento de Ingeniería Química, Universidad Nacional del Sur e Instituto de Ing. Electroquímica y Corrosión (INIEC), Av. Alem 1253, 8000 Bahía Blanca, Argentina;2. Departamento de Física, Universidad Nacional del Sur & IFISUR (UNS – CONICET), Av. Alem 1253, 8000 Bahía Blanca, Argentina;1. Pontificia Universidad Católica de Chile, Av.V. Mackenna 4860-Macul, BP 7820436, Santiago, Chile;2. Institut des Matériaux Jean Rouxel (IMN), CNRS, UMR 6502, 2 Rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3, France;3. Departamento de Química y Biología, Facultad de Ciencias Naturales, Universidad de Atacama, Copayapu 485, Copiapó, Chile;4. MOLTECH-Anjou, CNRS, UMR 6200, Université de Nantes, 2 Rue de la Houssinière, BP 92208, Nantes, F-44000, France |
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| Abstract: | ![]()
A new ground state potential energy surface has been developed for the F+H2 reaction. Using the UCCSD(T) method, ab initio calculations were performed for 786 geometries located mainly in the exit channel of the reaction. The new data was used to correct exit channel errors that have become apparent in the potential energy surface of Stark and Werner [J. Chem. Phys. 104 (1996) 6515]. While the entrance channel and saddlepoint properties of the Stark–Werner surface are unchanged on the new potential, the exit channel behavior is more satisfactory. The exothermicity on the new surface is much closer to the experimental value. The new surface also greatly diminishes the exit channel van der Waals well that was too pronounced on the Stark–Werner surface. Several preliminary dynamical scattering calculations were carried out using the new surface for total angular momentum equal to zero for F+H2 and F+HD. It is found that gross features of the reaction dynamics are quite similar to those predicted by the Stark–Werner surface, in particular the reactive resonance for F+HD and F+H2 survive. However, the most of the exit channel van der Waals resonances disappear on the new surface. It is predicted that the differential cross-sections at low collision energy for the F+H2 reaction may be drastically modified from the predictions based on the Stark–Werner surface. |
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