Showing papers in "Annual Review of Physical Chemistry in 1998"
TL;DR: An emphasis is put on the combination set-up of surface plasmon optics with electrochemical techniques, allowing for the on-line characterization of various surface functionalization strategies, e.g. for (bio-) sensor purposes.
Abstract: This contribution summarizes the use of plasmon surface polaritons and guided optical waves for the characterization of interfaces and thin organic films. After a short introduction to the theoretical background of evanescent wave optics, examples are given that show how this interfacial “light” can be employed to monitor thin coatings at a solid/air or solid/liquid interface. Examples are given for a very sensitive thickness determination of samples ranging from self-assembled monolayers, to multilayer assemblies prepared by the Langmuir/Blodgett/Kuhn technique or by the alternate polyelectrolyte deposition. These are complemented by the demonstration of the potential of the technique to also monitor time-dependent processes in a kinetic mode. Here, we put an emphasis on the combination set-up of surface plasmon optics with electrochemical techniques, allowing for the online characterization of various surface functionalization strategies, e.g. for (bio-) sensor purposes.
958 citations
TL;DR: Methods for the evaluation of these rate constants are discussed that are based on dielectric continuum theory and the rate-constant expressions corresponding to the ETPT and ET/PT channels for several model reaction complexes are evaluated.
Abstract: Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several areas where the transfer of an electron and proton is tightly coupled and discuss model systems that can provide an experimental basis for a test of PCET theory. In a PCET reaction, the electron and proton may transfer consecutively (ET/PT) or concertedly (ETPT). The distinction between these processes is formulated, and rate-constant expressions for the two reaction channels are presented. Methods for the evaluation of these rate constants are discussed that are based on dielectric continuum theory. Electron donor hydrogen-bonded-interface electron acceptor systems displaying PCET reactivity are presented, and the rate-constant expressions corresponding to the ETPT and ET/PT channels for several model reaction complexes are evaluated.
767 citations
TL;DR: Recent developments in optical studies of single molecules at room temperature are reviewed, with an emphasis on the underlying principles and the potential of single-molecule experiments.
Abstract: Recent developments in optical studies of single molecules at room temperature are reviewed, with an emphasis on the underlying principles and the potential of single-molecule experiments. Examples of single-molecule studies are given, including photophysics and photochemistry pertinent to single-molecule measurements, spectral fluctuations, Raman spectroscopy, diffusional motions, conformational dynamics, fluorescence resonant energy transfer, exciton dynamics, and enzymatic turnovers. These studies illustrate the information obtainable with the single-molecule approach that is hidden in ensemble-averaged measurements.
613 citations
TL;DR: The multiconfiguration self-consistent field method offers the most general approach to the computation of chemical reactions and multiple electronic states and localized orbitals are convenient both for selection of the appropriate active space and for understanding the computed results.
Abstract: The multiconfiguration self-consistent field (MCSCF) method offers the most general approach to the computation of chemical reactions and multiple electronic states. This review discusses the design of MCSCF wavefunctions for treating these problems and the interpretation of the resulting orbitals and configurations. In particular, localized orbitals are convenient both for selection of the appropriate active space and for understanding the computed results. The computational procedures for optimizing these wavefunctions and the techniques for recovery of dynamical correlation energy are reviewed.
612 citations
TL;DR: Within the past three years, a wide variety of molecules, ranging from OCS to large organic molecules such as amino acids and a number of van der Waals complexes and even large metal clusters, have been embedded in He droplets and studied either in infrared or in the visible region.
Abstract: ▪ Abstract Laser ablation of in situ metals has recently made it possible to immerse a large number of different metal atoms and ions and small clusters of metal atoms in liquid helium (He) and thus study their absorption and emission spectra in the visible region. Atoms and molecules are readily picked up by large ( ≥ 103 atoms) He droplets, and their spectra are sensitively detected through the use of either beam depletion following absorption or laser-induced fluorescence. Within the past three years, a wide variety of molecules, ranging from OCS to large organic molecules such as amino acids and a number of van der Waals complexes and even large metal clusters, have been embedded in He droplets and studied either in infrared or in the visible region. These results are discussed here in detail, and the evidence for the effect of superfluidity on the spectral features is reviewed.
486 citations
TL;DR: The detection of explosives, energetic materials, and their associated compounds for security screening, demining, detection of unexploded ordnance, and pollution monitoring is an active area of research.
Abstract: The detection of explosives, energetic materials, and their associated compounds for security screening, demining, detection of unexploded ordnance, and pollution monitoring is an active area of research. A wide variety of detection methods and an even wider range of physical chemistry issues are involved in this very challenging area. This review focuses on techniques such as optical and mass spectrometry and chromatography for detection of trace amounts of explosives with short response times. We also review techniques for detecting the decomposition fragments of these materials. Molecular data for explosive compounds are reviewed where available.
414 citations
TL;DR: In this article, various forms of photon echo (time-integrated, time-gated, and heterodyne-detected photon echo) as well as Fourier transform spectral interferometry are discussed.
Abstract: Chemical reaction and optical dynamics in the liquid phase are strongly affected by specific solute-solvent interactions. The dynamical part of this coupling leads to energy fluctuations. The associated energy gap dynamics can be probed by using various nonlinear optical spectroscopies. We discuss various forms of photon echo—time-integrated, time-gated, and heterodyne-detected photon echo—as well as Fourier transform spectral interferometry. It is shown that for solutions of the dye molecule DTTCI, a system-bath correlation function can be acquired that provides a quantitative description of all (non)linear spectroscopic experiments. The deduced correlation function is projected onto the multimode Brownian oscillator model, which allows for a physical interpretation of the multiple-time correlation function and a determination of the spectral density relevant to the solvation process. The following applications of photon echo to condensed phase dynamics are discussed: enhanced vibrational mode suppression, Liouville pathways interference, and dynamical Stokes shift. Recent results of echo-peak shift experiments on the hydrated electron are also presented. The review concludes that photon echo should be useful as a novel tool to explore transition state dynamics.
282 citations
TL;DR: Development of the sophisticated technology described in this review to handle the long-range electrostatic interactions has increased the predictive power of these simulations to the point where comparisons between explicit and continuum solvent models can reveal differences that have their true physical origin in the inherent molecularity of the surrounding medium.
Abstract: This review focuses on recent progress in two areas in which computer simulations with explicit solvent are being applied: the thermodynamic decomposition of free energies, and modeling electrostatic effects. The computationally intensive nature of these simulations has been an obstacle to the systematic study of many problems in solvation thermodynamics, such as the decomposition of solvation and ligand binding free energies into component enthalpies and entropies. With the revolution in computer power continuing, these problems are ripe for study but require the judicious choice of algorithms and approximations. We provide a critical evaluation of several numerical approaches to the thermodynamic decomposition of free energies and summarize applications in the current literature. Progress in computer simulations with explicit solvent of charge perturbations in biomolecules was slow in the early 1990s because of the widespread use of truncated Coulomb potentials in these simulations, among other factors. Development of the sophisticated technology described in this review to handle the long-range electrostatic interactions has increased the predictive power of these simulations to the point where comparisons between explicit and continuum solvent models can reveal differences that have their true physical origin in the inherent molecularity of the surrounding medium.
256 citations
TL;DR: The experiments reviewed here investigate how the breakdown of the Born-Oppenheimer approximation at a barrier along an adiabatic reaction coordinate can alter the dynamics of and the expected branching between molecular dissociation pathways.
Abstract: ▪ Abstract To predict the branching between energetically allowed product channels, chemists often rely on statistical transition state theories or exact quantum scattering calculations on a single adiabatic potential energy surface. The potential energy surface gives the energetic barriers to each chemical reaction and allows prediction of the reaction rates. Yet, chemical reactions evolve on a single potential energy surface only if, in simple terms, the electronic wavefunction can evolve from the reactant electronic configuration to the product electronic configuration on a time scale that is fast compared to the nuclear dynamics through the transition state. The experiments reviewed here investigate how the breakdown of the Born-Oppenheimer approximation at a barrier along an adiabatic reaction coordinate can alter the dynamics of and the expected branching between molecular dissociation pathways. The work reviewed focuses on three questions that have come to the forefront with recent theory and exper...
229 citations
TL;DR: This review discusses new approaches that are capable of initiating and monitoring the fast events in protein folding with temporal resolution down to picoseconds and the first important results from those techniques, which have been obtained for some globular proteins and polypeptide models.
Abstract: Most experimental studies on the dynamics of protein folding have been confined to timescales of 1 ms and longer. Yet it is obvious that many phenomena that are obligatory elements of the folding process occur on much faster timescales. For example, it is also now clear that the formation of secondary and tertiary structures can occur on nanosecond and microsecond times, respectively. Although fast events are essential to, and sometimes dominate, the overall folding process, with a few exceptions their experimental study has become possible only recently with the development of appropriate techniques. This review discusses new approaches that are capable of initiating and monitoring the fast events in protein folding with temporal resolution down to picoseconds. The first important results from those techniques, which have been obtained for the folding of some globular proteins and polypeptide models, are also discussed.
201 citations
TL;DR: Experiments in which the dynamical behavior of these monolayers has been monitored as a function of time both statically and after the introduction of an external perturbation are described, and novel studies of the selective control of monolayer structure that make use of internal and external electric fields, photons, and solvent coadsorption are reviewed.
Abstract: ▪ Abstract The imaging and control of self-assembled, physisorbed monolayers have been the subject of numerous scanning tunneling microscopy and atomic force microscopy investigations. The successful interpretation of the structures observed in scanning probe images of molecules self-assembled at liquid-solid and gas-solid interfaces has benefited greatly from recent experimental and theoretical work. These studies are converging on a general tunneling mechanism that accounts for the images of weakly bound, insulating adsorbates. Experiments in which the dynamical behavior of these monolayers has been monitored as a function of time both statically and after the introduction of an external perturbation are described, and novel studies of the selective control of monolayer structure that make use of internal and external electric fields, photons, and solvent coadsorption are reviewed.
TL;DR: Experimental results from hole-burning, single-molecule, photon echo, and resonance Raman and fluorescence studies are focused on, and the role of coupling of solvent phonons to the solute's electronic transition is stressed.
Abstract: The magnitudes, time scales, and underlying mechanisms responsible for broadening the electronic spectra of molecules in liquid solutions and glasses are reviewed. The emphasis is on experimental results from hole-burning, single-molecule, photon echo, and resonance Raman and fluorescence studies. The influence of the time scale of the measurement in distinguishing between homogeneous broadening (electronic dephasing) and inhomogeneous broadening is discussed, and the role of coupling of solvent phonons to the solute's electronic transition is stressed.
TL;DR: A review of recent high-resolution microwave, infrared, and optical spectroscopy experiments demonstrates that remarkable progress has been made in the past 20 years in determining the equilibrium geometries of large polyatomic molecules and their clusters in the gas phase, and how these geometry change when the photon is absorbed.
Abstract: A review of recent high-resolution microwave, infrared, and optical spectroscopy experiments demonstrates that remarkable progress has been made in the past 20 years in determining the equilibrium geometries of large polyatomic molecules and their clusters in the gas phase, and how these geometries change when the photon is absorbed. A special focus is on the dynamical information that can be obtained from such studies, particularly of electronically excited states.
IBM1
TL;DR: A critical review is presented of results obtained with different computational methods on C60, C70, and specific fullerene derivatives, also in comparison with experimental data, to establish a basis for a nonsuperficial reading of the existing literature and for a constructive approach with computations to the challenge posed by recent promising applications of fullerenes in nanotechnology, optoelectronics, and biology.
Abstract: ▪ Abstract A critical review is presented of results obtained with different computational methods (mainly ab initio) on C60, C70, and specific fullerene derivatives, also in comparison with experimental data. From the discussion of diverse systems, the (often underestimated) complexity of their physical and chemical behavior emerges, and hence the importance of an accurate description and the need for a careful inspection of the experimental data, with which comparison is often intrinsically difficult. The ambition of this review is to help establish a basis not only for a nonsuperficial reading of the existing literature, but also for a constructive approach with computations to the challenge posed by recent promising applications of fullerenes in nanotechnology, optoelectronics, and biology.
TL;DR: The principal techniques brought to bear are electron diffraction analyses of transformations in clusters formed by condensation of vapor in supersonic expansions and computer simulations of spontaneous phase changes in clusters.
Abstract: This paper reviews investigations of homogeneous nucleation in phase transitions in large molecular clusters. The principal techniques brought to bear are electron diffraction analyses of transformations in clusters formed by condensation of vapor in supersonic expansions and computer simulations of spontaneous phase changes in clusters. Results obtained to date are contrasted with those of larger systems and interpreted in terms of nucleation theory. The review also refers to some unresolved aspects of nucleation theory.
TL;DR: This review summarizes the observations as well as the current explanation for the glow, namely its being due to NO2* formed in surface-aided recombination between O and NO.
Abstract: ▪ Abstract Spacecraft in low earth orbit exhibit an unusual phenomenon: Surfaces facing the atmospheric wind produce a bright orange glow. This phenomenon was first noticed on the space shuttle but has since been verified as occurring on all spacecraft. The intensity of the glow depends on atmospheric density, on the angle between the velocity vector and the spacecraft surface, and on the temperature of the surface. This review summarizes the observations as well as the current explanation for the glow, namely its being due to NO*2 formed in surface-aided recombination between O and NO. Laboratory measurements and surface studies related to the phenomenon are briefly discussed.
TL;DR: My interest in the chemical elements and their compounds has prompted me to learn more about the nature of matter through the measurement and interpretation of optical, electric, and magnetic properties of molecules, which tell us about charge and current distributions.
Abstract: ▪ Abstract Physical chemistry and theoretical chemistry have advanced over the past 50 years from being largely qualitative to having a mature status based firmly on the principles of quantum and statistical mechanics. My interest in the chemical elements and their compounds has prompted me to learn more about the nature of matter through the measurement and interpretation of optical, electric, and magnetic properties of molecules. In addition to holding intrinsic interest, such properties tell us about charge and current distributions and form the basis of electro-optics, magneto-optics, and nonlinear optics. They also help us understand the nature and strength of long-range intermolecular forces, the hydrogen bond, and molecular biology—topics that are apparently forever young.