Location and energetics of transition states for the reactions H+ClF, H+FCl, H+F2, and H+Cl2

The potential energy surfaces of the reactions H+ClF→Hcl+F, H+FCl→HF+Cl, H+F2→HF+F, and H+Cl2→HCl+Cl have been investigated using ab initio molecular orbital theory. Calculations were done using polarized double zeta basis sets as the SOGVB+POL–CI level. The barrier heights uncorrected for zero‐point effects for the above reactions are 3.2, 9.6, 5.2, and 2.9 kcal/mol, respectively. The transition states for the H+F2 and H+FCl reactions are found to be collinear, while the transition states for the H+FClF and H+Cl2 reactions are found to be bent. The potential surface for a hydrogen migrating from Cl to F in the region of the transition state for H+ClF was found to be very repulsive.

[1]  D. Truhlar,et al.  Erratum: Monte Carlo trajectories: The reaction H+Br2→HBr+Br , 1976 .

[2]  P. Hay,et al.  Polarization CI wavefunctions: the valence states of the NH radical , 1976 .

[3]  William A. Goddard,et al.  The generalized valence bond description of O2 , 1975 .

[4]  J. Polanyi,et al.  Energy distribution among reaction products. H + NOCl, H + ICl , 1974 .

[5]  C. Bender,et al.  Saddle point geometry and barrier height for H + F2 → HF + F , 1974 .

[6]  W. Goddard,et al.  Generalized valence bond description of bonding in low-lying states of molecules , 1973 .

[7]  R. Raffenetti,et al.  General contraction of Gaussian atomic orbitals: Core, valence, polarization, and diffuse basis sets; Molecular integral evaluation , 1973 .

[8]  J. D. Mcdonald,et al.  Molecular Beam Kinetics: Reactions of Deuterium Atoms with Halogen Molecules , 1972 .

[9]  A. Dodonov,et al.  Mass‐Spectrometric Determination of Rate Constants for H‐Atom Reactions with Cl2 and F2 , 1969 .

[10]  J. L. Dunham.  The Wentzel-Brillouin-Kramers Method of Solving the Wave Equation , 1932 .

[11]  R. Raffenetti,et al.  A theoretical study of the potential energy surface for O(3P)+H2 , 1980 .

[12]  J. Polanyi,et al.  Distribution of reaction products (theory). Part 12.—Microscopic branching in H + XY → HX + Y, HY + X (X, Y = halogens) , 1979 .

[13]  A. Dedieu.  Surface d'énergie potentielle ab-initio pour la réaction colinéaire H + Cl2 → HCl + Cl , 1974 .

[14]  George S. Hammond,et al.  A Correlation of Reaction Rates , 1955 .

[15]  G. Herzberg.  Molecular Spectra and Molecular Structure IV. Constants of Diatomic Molecules , 1939 .