Classical potential energy as a function of the reaction coordinate, . Solid line: CCSD(t)/cc-pVTZ reaction path; dotted line: analytical PES reaction path.
Vibrational frequencies as functions of the reaction coordinate. Solid line: CCSD(t)/cc-pVTZ values; dashed line: analytical PES frequencies.
Changes in the energy of the saddle point [optimized at the CCSD(t)/cc-pVTZ level] as the angle is bent from linear to 90°. The zero of energy is set at the energy of the saddle point geometry optimized at the CCSD(t)/cc-pVTZ level. Solid line: CCSD(t)/cc-pVTZ energies; dashed line: analytical PES energies.
Contour plots of the analytical PES and CCSD(t)/cc-pVTZ surface in the proximity of the saddle point. The symbol × indicates the location of the CCSD(t)/cc-pVTZ saddle point, while the symbol ○ is the saddle point in the analytical PES.
Classical potential energy along the reaction path as a function of the (left panel) and (right panel) bond distances. Solid line: CCSD(t)/cc-pVTZ values; dotted line: analytical PES values.
Vibrationally adiabatic ground-state energy as a function of the reaction coordinate. The zero of energy is located at the reactants classical potential energy. Solid line: CCSD(t)/cc-pVTZ energies; dotted line: analytical PES energies.
Transmission probabilities and Boltzmann-averaged transmission probabilities computed using the small-curvature tunneling method as a function of the total energy at 250, 350, and 500 K. The zero of energy is located at the reactants potential energy. Solid line: CCSD(t)/cc-pVTZ probabilities; dashed line: analytical PES probabilities.
Saddle point geometry and energy parameters for the abstraction reaction. (Distances in Å; is the imaginary frequency, in , , is the classical energy of reaction, is the reaction enthalpy at 0 K, is the classical barrier height, is the activation enthalpy at 0 K. All energy values in .)
Parameters of the new PES.
Properties of the stationary points. (Geometries in Å and degrees, frequencies in , energies in and measured with respect to reactants, is the hydrogen being transferred, and the attacking hydrogen. The ab initio level used is CCSD(T)/cc-pVTZ.)
Rate and equilibrium constants. (Rate constants in , equilibrium constants are dimensionless. In parentheses, percentage of reaction that occurs by tunneling.)
Selected KIEs computed using the PES and ab initio rate constants. (KIEs are defined as the rate for the perprotio reaction over the overall rate for the reaction given in parentheses.)
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