Quantum instanton evaluation of the thermal rate constants and kinetic isotope effects for SiH4+H > SiH3+H2 reaction in full Cartesian space
ABSTRACT The quantum instanton calculations of thermal rate constants for the gasphase reaction SiH4+H>SiH3+H2 and its deuterated analogs are presented, using an analytical potential energy surface. The quantum instanton approximation is manipulated by full dimensionality in Cartesian coordinate path integral Monte Carlo approach, thereby taking explicitly into account the effects of the whole rotation, the vibrotational coupling, and anharmonicity of the reaction system. The rates and kinetic isotope effects obtained for the temperature range of 2001000 K show good agreements with available experimental data, which give support to the accuracy of the underlying potential surface used. In order to investigate the sole quantum effect to the rates, the authors also derive the classical limit of the quantum instanton and find that it can be exactly expressed as the classical variation transition state theory. Comparing the quantum quantities with their classical analogs in the quantum instanton formula, the authors demonstrate that the quantum correction of the prefactor is more important than that of the activation energy at the transition state.

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ABSTRACT: The dissociation and recombination rates of physisorbed H2, and the direct and steady state dissociation (i.e., the precursor mediated dissociation) rates of gas phase H2 on the Ni(111), as well as the corresponding kinetic isotope effects, are calculated with the quantum instanton method, together with path integral Monte Carlo and adaptive umbrella sampling techniques. All these rates except the recombination one first decrease and then increase with the increasing of temperature, and their minimum values appear at about 250, 300 and 250 K, respectively. These nonmonotonic behaviors reveal that the quantum effect of H2 should be very remarkable at low temperatures. The steady state rates are smaller than the direct rates at low temperatures, however, they become larger than the direct ones at high temperatures, these two kinds of rates become equal at about 400 and 300 K on the rigid and quantum lattices, respectively. The quantum motion of lattice can enhance the direct and steady state rates, and it increases the steady state rate much more than the direct one, for instance, the direct and steady state rates on the quantum lattice are 1.30 and 2.08 times larger than that on the rigid one at 300 K. The calculated kinetic isotope effects are much larger than 1, which reveals that H2 always has a larger rate than that of D2, and the direct process predicts much larger kinetic isotope effects than the steady state process at low temperatures. In addition, the kinetic isotope effects are not affected by the lattice motion.Physical Chemistry Chemical Physics 01/2015; DOI:10.1039/C4CP05624H · 4.20 Impact Factor 
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ABSTRACT: The rate constants and kinetic isotope effects of H2 dissociation and recombination on Ni(100) surface are calculated by using the quantum instanton method, together with path integral Monte Carlo and adaptive umbrella sampling techniques. The Ni(100) surface model containing 104 nickel atoms and the potential energy surface based on the embedded diatomics in molecules are used. For the H2 dissociation, the results on the rigid lattice are consistent with experimental data. Compared to the rigid lattice, the classical and quantum motions of the lattice further enhance the dissociation rates by 18 and 49% at 300 K. The calculated kinetic isotope effects show that the H2 always has the largest rate, while the D2 has the smallest one. For the H2 recombination, however, the effects of lattice motions on the rates are different from those for the dissociation, that is, compared to the rigid lattice, both the classical and quantum motions of the lattice lower the recombination rates. The possible mechanism is analyzed by the corresponding free energy profiles.The Journal of Physical Chemistry C 09/2013; 117(37):19010–19019. DOI:10.1021/jp406000f · 4.84 Impact Factor 
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ABSTRACT: The dissociation and recombination rates of physisorbed H2, and the total dissociation rate of gas phase H2 on the rigid Ni(100) surface, as well as the corresponding kinetic isotope effects, are calculated by using the quantum instanton method, together with path integral Monte Carlo and adaptive umbrella sampling techniques. Both the dissociation and recombination rates of physisorbed H2 are dramatically enhanced by the quantum motions of H2 at low temperatures, for instance, the quantum rates are 43 and 7.5 times larger than the classical ones at 200 K, respectively. For the dissociation of gas phase H2, at high temperatures, the H2 can fly over the physisorbed state and dissociate directly, however, at low temperatures, the H2 is first physisorbed and then dissociates under steady state approximation. The total dissociation rate of gas phase H2 can be expressed as a combination of the direct and steady state dissociation rates. It has the form of an inverted bell with a minimum value at about 400 K, and detailed analysis shows that the dissociation of gas phase H2 is dominated by a steady state process below 400 K, however, both the steady state and direct processes are important above 400 K. The calculated kinetic isotope effects reveal that H2 always has larger rates than D2 no matter which dissociative process they undergo.Physical Chemistry Chemical Physics 05/2014; 16(26). DOI:10.1039/c4cp01705f · 4.20 Impact Factor