1. Understanding chemical reactions at the molecular level 2. Molecular collisions 3. Introduction to reactive molecular collisions 4. Scattering as a probe of collision dynamics 5. Introduction to polyatomic dynamics 6. Structural considerations in the calculation of reaction rates 7. Photoselective chemistry: access to the transition state region 8. Chemistry in real time 9. State-changing collisions: molecular energy transfer 10. Stereodynamics 11. Dynamics in the condensed phase 12. Dynamics of gas-surface interactions and reactions.

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Effect of reagent rotation on elementary bimolecular exchange reactions

Molecular reaction dynamics

Molecular Reaction Dynamics: Frontmatter

We have investigated the dependence on the rotational and vibrational states of the translational energy of D2(v,J) formed in recombinative desorption from Cu(111). These results provide information about the effect of rotational energy relative to that of vibrational and translational energy on the dissociative chemisorption of D2 on Cu(111). The range of rovibrational states measured includes rotational states J=0–14 for vibrational state v=0, J=0–12 for v=1, and J=0–8 for v=2. D2 molecules were detected in a quantum‐state‐specific manner using three‐photon resonance‐enhanced multiphoton ionization (2+1 REMPI). Kinetic energies of desorbed molecules were obtained by measuring the flight time of D2+ ions in a field‐free region. The mean kinetic energies determined from these measurements depend strongly on the rotational and vibrational states. Analyzing these results using the principle of detailed balance confirms previous observations that vibrational energy is effective, though not as effective as tr...

Effect of rotation on the translational and vibrational energy dependence of the dissociative adsorption of D2 on Cu(111)

Rate constants for the reactions of Kr+(2P3/2) with HCl and DCl and of Ar+ with HCl have been measured as a function of reactant ion/reactant neutral average center‐of‐mass kinetic energy (〈KEc.m.〉 ) at several temperatures. The measurements were made using helium as the carrier gas. From these data we have derived the dependences of the rate constants on the rotational temperature of H(D)Cl. Rate constants for the reaction of Kr+(2P1/2) with HCl have also been measured as a function of temperature. The rate constants for all of the reactions were found to decrease with increasing temperature. The rate constants were also found to decrease with increasing 〈KEc.m.〉 at low 〈KEc.m.〉 but then to increase at higher 〈KEc.m.〉 . A significant rotational temperature dependence of the rate constant was derived for the reaction of Kr+(2P3/2) with H(D)Cl. The analogous derivation for Ar+ reacting with HCl showed the rate constant for this reaction to be independent of the rotational temperature of HCl within experimental uncertainty.

Kinetic energy, temperature, and derived rotational temperature dependences for the reactions of Kr+(2P3/2) and Ar+ with HCl

Three dimensional quasiclassical trajectory calculations were carried out for the nearly thermoneutral reaction of oxygen atoms O(3P) with hydrogen chloride molecules (HCl and DC1), for reaction temperatures of 300 and 700 K, employing two LEPS potential energy surfaces. Calculations for 300 K were performed for various initial vibrational states of the reagents HCl(ν=0, 1, 2, and 4) and DC1(ν=0 and 1). Calculations for 700 K were carried out for the ground vibrational state ν=0. The effect of rotational excitation on reactivity was investigated by calculating reaction cross sections for specific initial rotational states for the reaction O+HCl(ν=0, J=0–19) for collision energies of 6.0 and 10.0 kcal/mol. The rate of the O+HCl reaction was found to be enhanced by more than two orders of magnitude (factors of 150 and 390 for the two surfaces used) for O+HCl(ν=1), and by more than three orders of magnitude for O+HCl(ν=2), as compared to O+HCl(ν=0). The influence of rotational excitation on reactivity was fo...

Quasiclassical trajectory study of the reaction O(3P)+HCl → OH+Cl. The effects of vibrational excitation, rotational excitation, and isotopic substitution on the dynamics

Effect of reagent rotation on elementary bimolecular exchange reactions

Citations

Molecular reaction dynamics

Molecular Reaction Dynamics: Frontmatter

Effect of rotation on the translational and vibrational energy dependence of the dissociative adsorption of D2 on Cu(111)

Kinetic energy, temperature, and derived rotational temperature dependences for the reactions of Kr+(2P3/2) and Ar+ with HCl

Quasiclassical trajectory study of the reaction O(3P)+HCl → OH+Cl. The effects of vibrational excitation, rotational excitation, and isotopic substitution on the dynamics

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