Potential Energy Surfaces and Dynamics Calculations: For Chemical Reactions and Molecular Energy Transfer

ISBN-13: 9781475717372 / Angielski / Miękka / 2013 / 866 str.

Donald Truhlar

Opis

The present volume is concerned with two of the central questions of chemical dynamics. What do we know about the energies of interaction of atoms and molecules with each other and with solid surfaces? How can such interaction energies be used to understand and make quantitative predictions about dynamical processes like scattering, energy transfer, and chemical reactions? It is becoming clearly recognized that the computer is leading to rapid progress in answering these questions. The computer allows probing dynamical mechanisms in fine detail and often allows us to answer questions that cannot be addressed with current experimental techniques. As we enter the 1980's, not only are more powerful and faster computers being used, but techniques and methods have been honed to a state where exciting and reliable data are being generated on a variety of systems at an unprecedented pace. The present volume presents a collection of work that illustrates the capabilities and some of the successes of this kind of computer-assisted research. In a 1978 Chemical Society Report, Frey and Walsh pointed out that "it is extremely doubtful if a calculated energy of activation for any unimolecular decomposition can replace an experimental deter mination. " However they also recorded that they "believe d] that some of the elaborate calculations being performed at present do suggest that we may be approaching a time when a choice between reaction mechanisms will be helped by such computational] work."

Spis treści

1. Overview of Unimolecular Dynamics.- 2. Effect of potential energy surface properties on unimolecular dynamics for a model alkyl radical dissociation reaction: H-C-C ? H + C=C.- 3. Vibrational predissociation of van der Waals molecules and intermolecular potential energy surfaces.- 4. Potential surface properties and dynamics from molecular spectra: A time-dependent picture.- 5. Calculation of potential energy surfaces for HCO and HNO using many-body methods.- 6. Theoretical studies on the unimolecular decomposition of methanol.- 7. Potential energy surfaces in excited states of saturated molecules.- 8. Interpolation of multidimensional potential surfaces by polynomial roots.- 9. Classical trajectory studies of the formation and unimolecular decay of rare gas clusters.- 10. Potential energy characteristics for chemical reactions.- 11. Reaction path Hamiltonian for polyatomic systems: Further developments and applications.- 12. Overview of Reactive Scattering.- 13. A quasiclassical trajectory study of product rotational, angular, and projection distributions in the OH + H2 ? H2O + H reaction.- 14. Theoretical studies of selected reactions in the hydrogen-oxygen system.- 15. Exact quantum reaction probabilities for the collinear O(3P) + H2 reaction on an Ab initio and diatomies-in-molecules potential surface.- 16. Reactive scattering resonances and their physical interpretation: The vibrational structure of the transition state.- 17. Quasiclassical differential cross sections for reactive scattering of H + H2 on LEPS and Porter-Karplus potential surfaces.- 18. Reaction, dissociation, and energy transfer as a function of initial state for H + H2 on an accurate ab initio potential energy surface.- 19. Rate constant calculations for the H + H2 and F + H2 reaction systems within the infinite-order sudden approximation.- 20. Quantum dynamics of the three-dimensional F +H2 reaction: Wavefunction density analysis.- 21. Potential energy surfaces for the H + HX (X = F, Cl, Br, I) abstraction and exchange reaction channels calculated by the modified DIM method.- 22. Potential energy surface and cross sections for the H?(D?) + H2(D2, HD) ion-molecule reactions.- 23. Reactions of the D state of oxygen and carbon.- 24. Determination of the bottleneck regions of potential energy surfaces for atom transfer reactions by variational transition state theory.- 25. Laser-induced nonadiabatic collision processes.- 26. Application of the energy minimization method to a search for the transition state for the H2 + D2 exchange reaction.- 27. Theoretical studies of reactions at transition metal centers.- 28. Overview of Non-Reactive Scattering.- 29. Scattering of ions by polyatomics and solid surfaces: Multicenter short-range interactions.- 30. On CC and CS descriptions of phase-sensitive cross sections: Computations for He + HCl.- 31. Rainbow scattering in inelastic molecular collisions.- 32. Effect of laser frequency on a collision-induced radiative process.- 33. Collisional excitation of H2O by O-atom impact: Classical dynamics on an accurate Ab initio potential energy surface.- 34. Interaction potentials for gas-surface dynamics.- 35. Atom-surface potential information from low-energy atom-surface scattering.- 36. Classical trajectory studies of keV ions interacting with solid surfaces.- Appendix: Units.