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7 Oct 2006

Volume 125, Issue 13, Articles (13xxxx)

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Preface: Chemical Dynamics

Donald H. Levy

J. Chem. Phys. 125, 132101 (2006); http://dx.doi.org/10.1063/1.2362815 (2 pages)

Online Publication Date: 3 October 2006

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Abstract Unavailable
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82.20.-w Chemical kinetics and dynamics
01.30.-y Physics literature and publications

Introduction: Chemical Dynamics

Cheuk-Yiu Ng

J. Chem. Phys. 125, 132201 (2006); http://dx.doi.org/10.1063/1.2358348 (2 pages)

Online Publication Date: 3 October 2006

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Abstract Unavailable
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82.20.-w Chemical kinetics and dynamics
01.60.+q Biographies, tributes, personal notes, and obituaries

Theories of reactive scattering

Wenfang Hu and George C. Schatz

J. Chem. Phys. 125, 132301 (2006); http://dx.doi.org/10.1063/1.2213961 (15 pages) | Cited 42 times

Online Publication Date: 2 October 2006

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This paper is an overview of the theory of reactive scattering, with emphasis on fully quantum mechanical theories that have been developed to describe simple chemical reactions, especially atom-diatom reactions. We also describe related quasiclassical trajectory applications, and in all of this review the emphasis is on methods and applications concerned with state-resolved reaction dynamics. The review first provides an overview of the development of the theory, including a discussion of computational methods based on coupled channel calculations, variational methods, and wave packet methods. Choices of coordinates, including the use of hyperspherical coordinates are discussed, as are basis set and discrete variational representations. The review also summarizes a number of applications that have been performed, especially the two most comprehensively studied systems, H+H2 and F+H2, along with brief discussions of a large number of other systems, including other hydrogen atom transfer reactions, insertion reactions, electronically nonadiabatic reactions, and reactions involving four or more atoms. For each reaction we describe the method used and important new physical insight extracted from the results.
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82.30.Cf Atom and radical reactions; chain reactions; molecule-molecule reactions
82.20.Db Transition state theory and statistical theories of rate constants
82.20.Gk Electronically non-adiabatic reactions
82.30.Nr Association, addition, insertion, cluster formation
82.30.Hk Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)
01.30.Rr Surveys and tutorial papers; resource letters

Infrared studies of ionic clusters: The influence of Yuan T. Lee

James M. Lisy

J. Chem. Phys. 125, 132302 (2006); http://dx.doi.org/10.1063/1.2338317 (19 pages) | Cited 27 times

Online Publication Date: 2 October 2006

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Beginning in the mid-1980s, a number of innovative experimental studies on ionic clusters emerged from the laboratory of Yuan T. Lee combining infrared laser spectroscopy and tandem mass spectrometry. Coupled with modern electronic structure calculations, this research explored many facets of ionic clusters including solvation, structure, and dynamics. These efforts spawned a resurgence in gas-phase cluster spectroscopy. This paper will focus on the major areas of research initiated by the Lee group and how these studies stimulated and influenced others in what is currently a vibrant and growing field.
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36.40.Wa Charged clusters
36.40.Mr Spectroscopy and geometrical structure of clusters
33.20.Ea Infrared spectra
33.15.Ta Mass spectra

Probing chemical dynamics with negative ions

Daniel M. Neumark

J. Chem. Phys. 125, 132303 (2006); http://dx.doi.org/10.1063/1.2216709 (15 pages) | Cited 25 times

Online Publication Date: 3 October 2006

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Experiments are reviewed in which key problems in chemical dynamics are probed by experiments based on photodetachment and/or photoexcitation of negative ions. Examples include transition state spectroscopy of biomolecular reactions, spectroscopy of open shell van der Waals complexes, photodissociation of free radicals, and time-resolved dynamics in clusters. The experimental methods used in these investigations are described along with representative systems that have been studied.
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82.20.Db Transition state theory and statistical theories of rate constants
82.30.Cf Atom and radical reactions; chain reactions; molecule-molecule reactions
82.50.-m Photochemistry
82.80.Dx Analytical methods involving electronic spectroscopy
33.80.Eh Autoionization, photoionization, and photodetachment
33.80.Gj Diffuse spectra; predissociation, photodissociation

State-to-state reaction dynamics: A selective review

Alexey Teslja and James J. Valentini

J. Chem. Phys. 125, 132304 (2006); http://dx.doi.org/10.1063/1.2354466 (22 pages) | Cited 12 times

Online Publication Date: 3 October 2006

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A selective review of state-to-state reaction dynamics experiments is presented. The review focuses on three classes of reactions that exemplify the rich history and illustrate the current state of the art in such work. These three reactions are (1) the hydrogen exchange reaction, H+H2→H2+H and its isotopomers; (2) the H+RH→H2+R reactions, where RH is an alkane, beginning with H+CH4→H2+CH3 and extending to much larger alkanes; and (3) the Cl+RH→HCl+R reactions, principally Cl+CH4→HCl+CH3. We describe the experiments, discuss their results, present comparisons with theory, and introduce heuristic models.
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82.30.Hk Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)
82.30.Cf Atom and radical reactions; chain reactions; molecule-molecule reactions
82.20.Bc State selected dynamics and product distribution

Including quantum effects in the dynamics of complex (i.e., large) molecular systems

William H. Miller

J. Chem. Phys. 125, 132305 (2006); http://dx.doi.org/10.1063/1.2211608 (8 pages) | Cited 47 times

Online Publication Date: 3 October 2006

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The development in the 1950s and 1960s of crossed molecular beam methods for studying chemical reactions at the single-collision molecular level stimulated the need and desire for theoretical methods to describe these and other dynamical processes in molecular systems. Chemical dynamics theory has made great strides in the ensuing decades, so that methods are now available for treating the quantum dynamics of small molecular systems essentially completely. For the large molecular systems that are of so much interest nowadays (e.g., chemical reactions in solution, in clusters, in nanostructures, in biological systems, etc.), however, the only generally available theoretical approach is classical molecular dynamics (MD) simulations. Much effort is currently being devoted to the development of approaches for describing the quantum dynamics of these complex systems. This paper reviews some of these approaches, especially the use of semiclassical approximations for adding quantum effects to classical MD simulations, also showing some new versions that should make these semiclassical approaches even more practical and accurate.
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82.30.Cf Atom and radical reactions; chain reactions; molecule-molecule reactions
82.20.Db Transition state theory and statistical theories of rate constants
82.20.Ln Semiclassical theory of reactions and/or energy transfer
82.20.Xr Quantum effects in rate constants (tunneling, resonances, etc.)

The study of state-selected ion-molecule reactions using the vacuum ultraviolet pulsed field ionization-photoion technique

Rainer A. Dressler, Y. Chiu, D. J. Levandier, X. N. Tang, Y. Hou, C. Chang, C. Houchins, H. Xu, and Cheuk-Yiu Ng

J. Chem. Phys. 125, 132306 (2006); http://dx.doi.org/10.1063/1.2207609 (14 pages) | Cited 15 times

Online Publication Date: 4 October 2006

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This paper presents the methodology to generate beams of ions in single quantum states for bimolecular ion-molecule reaction dynamics studies using pulsed field ionization (PFI) of atoms or molecules in high-n Rydberg states produced by vacuum ultraviolet (VUV) synchrotron or laser photoexcitation. Employing the pseudocontinuum high-resolution VUV synchrotron radiation at the Advanced Light Source as the photoionization source, PFI photoions (PFI-PIs) in selected rovibrational states have been generated for ion-molecule reaction studies using a fast-ion gate to pass the PFI-PIs at a fixed delay with respect to the detection of the PFI photoelectrons (PFI-PEs). The fast ion gate provided by a novel interleaved comb wire gate lens is the key for achieving the optimal signal-to-noise ratio in state-selected ion-molecule collision studies using the VUV synchrotron based PFI-PE secondary ion coincidence (PFI-PESICO) method. The most recent development of the VUV laser PFI-PI scheme for state-selected ion-molecule collision studies is also described. Absolute integral cross sections for state-selected H2+ ions ranging from v+ = 0 to 17 in collisions with Ar, Ne, and He at controlled translational energies have been obtained by employing the VUV synchrotron based PFI-PESICO scheme. The comparison between PFI-PESICO cross sections for the H2+(HD+)+Ne and H2+(HD+)+He proton-transfer reactions and theoretical cross sections based on quasiclassical trajectory (QCT) calculations and three-dimensional quantum scattering calculations performed on the most recently available ab initio potential energy surfaces is highlighted. In both reaction systems, quantum scattering resonances enhance the integral cross sections significantly above QCT predictions at low translational and vibrational energies. At higher energies, the agreement between experiment and quasiclassical theory is very good. The profile and magnitude of the kinetic energy dependence of the absolute integral cross sections for the H2+(v+ = 0–2,N+ = 1)+He proton-transfer reaction unambiguously show that the inclusion of Coriolis coupling is important in quantum dynamics scattering calculations of ion-molecule collisions.
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82.30.Fi Ion-molecule, ion-ion, and charge-transfer reactions
82.30.Hk Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)
82.20.Kh Potential energy surfaces for chemical reactions
82.20.Fd Collision theories; trajectory models
32.80.Fb Photoionization of atoms and ions
33.80.Eh Autoionization, photoionization, and photodetachment

Recent advances in crossed-beam studies of bimolecular reactions

Kopin Liu

J. Chem. Phys. 125, 132307 (2006); http://dx.doi.org/10.1063/1.2216706 (12 pages) | Cited 21 times

Online Publication Date: 5 October 2006

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A critical overview of the recent progress in crossed-beam reactive scattering is presented. This review is not intended to be an exhaustive nor a comprehensive one, but rather a critical assessment of what we have been learning about bimolecular reaction dynamics using crossed molecular beams since year 2000. Particular emphasis is placed on the information content encoded in the product angular distribution—the trait of a typical molecular beam scattering experiment—and how the information can help in answering fundamental questions about chemical reactivity. We will start with simple reactions by highlighting a few benchmark three-atom reactions, and then move on progressively to the more complex chemical systems and with more sophisticated types of measurements. Understanding what cause the experimental observations is more than computationally simulating the results. The give and take between experiment and theory in unraveling the physical picture of the underlying dynamics is illustrated throughout this review.
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82.40.-g Chemical kinetics and reactions: special regimes and techniques
82.30.Cf Atom and radical reactions; chain reactions; molecule-molecule reactions
82.20.-w Chemical kinetics and dynamics
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