The Journal of Chemical Physics · 1964 · 667 citations · 14 references
Natural SciencesChemistryPhysicsPhysical ChemistryQuantum ChemistryTheoretical ChemistryAb Initio MethodsInteratomic PotentialsMolecular Orbital TheoryMolecular SymmetryPotential Energy SurfacesSurface EnergyAb Initio Potential Energy SurfacesAnalytic Potential Energy SurfacesCoulomb InteractionExchange IntegralsMolecular Potential Energy SurfacesPotential Energy Surface ConstructionPotential Energy TermsReaction Cross Sections
An analytic semiempirical expression is developed for the ground‑state potential‑energy surface of the H3 system. The authors construct the surface using a valence‑bond approach that incorporates overlap and three‑center terms, estimating diatomic integrals from H2 data via a modified London–Eyring–Sato procedure and approximating three‑center integrals with simple formulas, and present the results as contour maps. The resulting surface predicts a linear, symmetric saddle‑point minimum whose properties roughly agree with other theoretical and experimental data, and the inclusion of overlap and three‑center terms yields more realistic energies for nonlinear configurations, suggesting usefulness for dynamical studies of reaction cross sections.
An analytic semiempirical expression is developed for the ground-state potential-energy surface of the H3 system. Use is made of the valence-bond formulation with the inclusion of overlap and three-center terms. The diatomic Coulomb and exchange integrals are estimated from accurate values for the H2 molecule by a modified London—Eyring—Sato procedure, while the three-center integrals are approximated by simple formulas. A linear, symmetric saddle-point configuration of minimum energy is found that has properties in approximate agreement, though not identical, with other estimates from theory and experimental rate data. The details of the surface are presented in terms of contour maps for a variety of distances and angles. Because of the inclusion of overlap and three-center terms, a more realistic energy is expected for the nonlinear configurations than could be obtained from previous potential energy formulas. The utility of the present method for dynamical studies of reaction cross sections is indicated.
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The Problem of the Normal Hydrogen Molecule in the New Quantum Mechanics
S. C. Wang · Physical Review · 1928 · 417 citations
Molecular Energy Levels and Valence Bonds
J. C. Slater · Physical Review · 1931 · 345 citations
Natural Sciences, Chemistry, Physics +15
A New Method of Drawing the Potential Energy Surface
Shin Sato · Bulletin of the Chemical Society of Japan · 1955 · 306 citations
Natural Sciences, Chemistry, Physics +17