Self-consistent-field potential energy surface in three dimensions for the Cl + H2 → ClH + H chemical reaction

✍ Scribed by S. Rothenberg; H.F. Schaefer III

• Publisher: Elsevier Science
• Year: 1971
• Tongue: English
• Weight: 484 KB
• Volume: 10
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(71)87038-0

✦ Synopsis

Non-empirical self-consistent-field calculations have been carried out for 38 points on the potential surface for the Cl f H, + ClH + H chemical reaction. A basis set of seven s, five p, and one d functions on ctiorine and three s and one p on each hydrogen atom was used. The least energy path r~ccurs for-the linear Cl-H-H arrangement. A much higher barrier is found for the approach of Cl along the H-H perpendicular bisector. The Iin& barrier height is predicted to be 26.2 kcal/mole and the saddle point occurs for R(Cl-H) = 1.46 d,R(H-HI) w 0.94 A. The experimental activation energy is 5.5 kcaJ/mole. It seems likely that a general feature of the HartreeLFock approximation is an overestimation of barrier heights. The exothermicity is calculated to be -6.7 kcal/mote. compared to the near Hartree-Fock result -2.3 kcal/mole and experiment -3.0 kcal/mob.