Annual Review of Physical Chemistry - Volume 55, 2004

This is the story of a native-born American who came as a postdoc to the country of his parents, Germany. There, by good fortune, he could participate in the revival and the rebuilding of the physical sciences following the ravishments of the Second World War, becoming at the age of 38, the director of a Max-Planck-Institut in Göttingen. Working under nearly ideal conditions, he carried out basic research using molecular beams. Aided by many active, youthfully impulsive, yet perceptive and imaginative, students and experienced knowledgeable guest scientists from many countries, he enjoyed exciting adventures into unknown landscapes in the fields of molecular gas-phase interactions and solid-surface phenomena and, most recently, in the realms of quantum liquids and solids.

The microscopic length scale and high surface-to-volume ratio, characteristic of microelectro-mechanical systems (MEMS), dictate that surface properties are of paramount importance. This review deals with the effects of surface chemical treatments on tribological properties (adhesion, friction, and wear) of MEMS devices. After a brief review of materials and processes that are utilized in MEMS technology, the relevant tribological and chemical issues are discussed. Various MEMS microinstruments are discussed, which are commonly employed to perform adhesion, friction, and wear measurements. The effects of different surface treatments on the reported tribological properties are discussed.

Progress in the study of a new class of chemically bound compounds of noble-gas atoms is reviewed. The focus is on rare-gas molecules of the form HNgY, where Ng is a noble-gas atom and Y is an electronegative group, prepared by photolysis of HY in the rare-gas matrix. Other related types of new molecules of noble-gas atoms are discussed as well. Topics discussed in this review include: (a) The nature of bonding and the energetic stability of the compounds. (b) The vibrational spectroscopy of the molecules, and its role in identification of the species. (c) The mechanism and dynamics of photochemical formation of HNgY in the matrix, and the pathways for thermal and infrared (IR)-induced decomposition. Specifically, attention is given to the issue of “direct” formation following photolysis of HY versus “delayed” formation involving H atom diffusion. (d) Molecules of the lighter rare gases Ar, Ne, and He, focusing on the experimentally prepared HArF and on theoretical predictions suggesting the existence of other molecules. (e) The most-recently discovered photochemically induced insertion compounds of Ng into hydrocarbons, such as HXeCCH. (f) Clusters of HNgY with other molecules. The possible existence of neat aggregates and crystals of HNgY.

The reviewed state-of-the-art suggests this field is at an early stage of development with major open questions bearing on the surprising properties of the molecules and on the formation mechanisms. These are part of the challenge for the future.

The methods of single-molecule fluorescence spectroscopy and microscopy have been recently utilized to explore the mechanism of action of several members of the kinesin and myosin biomolecular motor protein families. Whereas ensemble averaging is removed in single-molecule studies, heterogeneity in the behavior of individual motors can be directly observed, without synchronization. Observation of translocation by individual copies of motor proteins allows analysis of step size, rate, pausing, and other statistical properties of the process. Polarization microscopy as a function of nucleotide state has been particularly useful in revealing new and highly rotationally mobile forms of particular motors. These experiments complement X-ray and biochemical studies and provide a detailed view into the local dynamical behavior of motor proteins.

Instrumental advances have allowed the continuous observation of single-molecule trajectories in free solution. Diffraction-limited spectral resolution at video frame rates is routinely achieved by using commercial, intensified, charge-coupled device cameras, low-power continuous-wave lasers, and standard optical microscopes. Either the native fluorescence from large biomolecules or emission from conjugated fluorescence labels can be employed to follow multiple molecules over many seconds. Both molecular motion at the liquid/solid interface and in bulk solution can be recorded. The former reveals adsorption and desorption probabilities that are related to chromatographic retention processes and to the applicability of biocompatible materials. The latter allows the manipulation of particles and large biomolecules to facilitate separation and identification.

Nonadiabatic effects play an important role in many areas of physics and chemistry. The coupling between electrons and nuclei may, for example, lead to the formation of a conical intersection between potential energy surfaces, which provides an efficient pathway for radiationless decay between electronic states. At such intersections the Born-Oppenheimer approximation breaks down, and unexpected dynamical processes result, which can be observed spectroscopically. We review the basic theory required to understand and describe conical, and related, intersections. A simple model is presented, which can be used to classify the different types of intersections known. An example is also given using wavepacket dynamics simulations to demonstrate the prototypical features of how a molecular system passes through a conical intersection.

Nanobelt is a quasi-one-dimensional structurally controlled nanomaterial that has well-defined chemical composition, crystallographic structure, and surfaces (e.g., growth direction, top/bottom surface, and side surfaces). This article reviews the nanobelt family of functional oxides, including ZnO, SnO2, In2O3, Ga2O3, CdO, and PbO2 and the relevant hierarchical and complex nanorods and nanowires that have been synthesized by a solid-vapor process. The nanobelts are single crystalline and dislocation free, and their surfaces are atomically flat. The oxides are semiconductors that have been used for fabrication of nanosize functional devices of key importance for nanosystems and biotechnology, such as field-effect transistors, gas sensors, nanoresonators, and nanocantilevers.

The structurally controlled ZnO nanobelts that exhibit piezoelectric properties are also reviewed. By controlling growth kinetics, we show the success of growing nanobelt-based novel structures whose surfaces are dominated by the polarized ±(0001) facets. Owing to the positive and negative ionic charges on the zinc- and oxygen-terminated ±(0001) surfaces, respectively, a spontaneous polarization is induced across the nanobelt thickness. As a result, helical nanostructures and nanorings are formed by rolling up single-crystal nanobelts; this phenomenon is a consequence of minimizing the total energy contributed by spontaneous polarization and elasticity. The polar surface–dominated ZnO nanobelts are likely to be an ideal system for understanding piezoelectricity and polarization-induced ferroelectricity at nano-scale and they could have applications as one-dimensional nano-scale sensors, transducers, and resonators.

Over the past three decades, surface-enhanced Raman spectroscopy (SERS) has gone through a tortuous pathway to develop into a powerful surface diagnostic technique for in situ investigation of surface adsorption and reactions on electrodes. This review presents the recent progress achieved mainly in our laboratory on the improvement of detection sensitivities as well as spectral, temporal, and spatial resolutions. Various surface roughening procedures for electrodes of different metals coupled with maximum use of a high-sensitivity confocal Raman microscope enable us to obtain good-quality SER spectra on the electrode surfaces made from net Pt, Ni, Co, Fe, Pd, Rh, Ru, and their alloys that were traditionally considered to be non-SERS active. A novel technique called potential-averaged SERS (PASERS) has been developed for the quantitative study of electrochemical sorption. Applications are exemplified on extensively studied areas such as coadsorption, electrocatalysis, corrosion, and fuel cells, and several advantages of in situ electrochemical SERS are demonstrated. Finally, further developments in this field are briefly discussed with emphasis on the emerging methodology.

Molecular beam scattering experiments provide a way to disentangle the elementary steps involved in energy transfer and chemical reactions between gases and liquids. After surveying the history and recent progress in this field, we review studies of the kinematics of gas-liquid collisions and proton exchange of HCl, DCl, and HBr with supercooled sulfuric acid and liquid glycerol. These experiments help to clarify the role of the surface region in controlling trapping and interfacial- and bulk-phase reactions.

Charge transport at conjugated polymer interfaces with metals and inorganic semiconductors is reviewed. Experiments on the equilibrium properties and DC current-voltage behavior of four specific classes of interfaces—metal–doped conjugated polymer, inorganic semiconductor–doped conjugated polymer, metal–intrinsic conjugated polymer, and metal–intrinsic conjugated polymer/electrolyte—are discussed. To facilitate this discussion, classic models of equilibration at ideal interfaces between electronic conductors and free-electron transport are introduced and their limitations discussed. Particular emphasis is placed on the charge distributions and interfacial potential profiles expected at various types of electroactive interfaces.

Recent progress in the development of semiclassical methods to describe quantum effects in molecular dynamics is reviewed. Focusing on rigorous semiclassical methods that are based on the initial-value representation of the semiclassical propagator, we discuss several promising schemes that have been developed in the past few years to extend the applicability of semiclassical approaches to complex molecular systems. In particular, integral-filtering techniques and forward-backward methods are surveyed. Furthermore, recently proposed approaches that allow the semiclassical description of nonadiabatic molecular dynamics are discussed. The potential and efficiency of these methods is illustrated by selected applications.

This review discusses the recent progress that has been made in the application of computer simulations to study crystal nucleation in colloidal systems. We discuss the concept and the numerical methods that allow for a quantitative prediction of crystal-nucleation rates. The computed nucleation rates are predicted from first principles and can be directly compared with experiments. These techniques have been applied to study crystal nucleation in hard-sphere colloids, polydisperse hard-sphere colloids, weakly charged or slightly soft colloids, and hard-sphere colloids that are confined between two-plane hard walls.

Proton-coupled electron transfer (PCET) reactions involve the concerted transfer of an electron and a proton. Such reactions play an important role in many areas of chemistry and biology. Concerted PCET is thermochemically more favorable than the first step in competing consecutive processes involving stepwise electron transfer (ET) and proton transfer (PT), often by ≥1 eV. PCET reactions of the form X–H + Y → X + H–Y can be termed hydrogen atom transfer (HAT). Another PCET class involves outersphere electron transfer concerted with deprotonation by another reagent, Y⁺ + XH–B → Y + X–HB⁺. Many PCET/HAT rate constants are predicted well by the Marcus cross relation. The cross-relation calculation uses rate constants for self-exchange reactions to provide information on intrinsic barriers. Intrinsic barriers for PCET can be comparable to or larger than those for ET. These properties are discussed in light of recent theoretical treatments of PCET.

Recent applications of neutron reflectometry to the study of wet interfaces are described. An outline is given of the basic principles that allow the techniques to determine composition and structure in a variety of situations. These are the adsorption of surfactant molecules at air/liquid and solid/liquid interfaces, the shape of the segment-density profiles of different types of polymer, including block copolymers and polyelectrolytes, adsorption in mixed surfactant and polymer/surfactant systems, and interfacial systems of biophysical interest.

Time-dependent density functional theory (TDDFT) can be viewed as an exact reformulation of time-dependent quantum mechanics, where the fundamental variable is no longer the many-body wave function but the density. This time-dependent density is determined by solving an auxiliary set of noninteracting Schrödinger equations, the Kohn-Sham equations. The nontrivial part of the many-body interaction is contained in the so-called exchange-correlation potential, for which reasonably good approximations exist. Within TDDFT two regimes can be distinguished: (a) If the external time-dependent potential is “small,” the complete numerical solution of the time-dependent Kohn-Sham equations can be avoided by the use of linear response theory. This is the case, e.g., for the calculation of photoabsorption spectra. (b) For a “strong” external potential, a full solution of the time-dependent Kohn-Sham equations is in order. This situation is encountered, for instance, when matter interacts with intense laser fields. In this review we give an overview of TDDFT from its theoretical foundations to several applications both in the linear and in the nonlinear regime.

Single-molecule spectroscopy (SMS) is a powerful experimental technique used to investigate a wide range of physical, chemical, and biophysical phenomena. The merit of SMS is that it does not require ensemble averaging, which is found in standard spectroscopic techniques. Thus SMS yields insight into complex fluctuation phenomena that cannot be observed using standard ensemble techniques. We investigate theoretical aspects of SMS, emphasizing (a) dynamical fluctuations (e.g., spectral diffusion, photon-counting statistics, antibunching, quantum jumps, triplet blinking, and nonergodic blinking) and (b) single-molecule fluctuations in disordered systems, specifically distribution of line shapes of single molecules in low-temperature glasses. Special emphasis is given to single-molecule systems that reveal surprising connections to Lévy statistics (i.e., blinking of quantum dots and single molecules in glasses). We compare theory with experiment and mention open problems. Our work demonstrates that the theory of SMS is a complementary field of research for describing optical spectroscopy in the condensed phase.

The review describes the studies of the magneto-optical properties of II-VI and III-V semiconductor nanocrystals (NCs) capped with organic or inorganic epitaxial shells. The investigations focused on the chemical identification of localization sites (core, shell, or interface) of photogenerated carriers in spherical NCs and elucidated the influence of the surface/interface quality on the optical properties of the materials. Optically detected magnetic resonance (ODMR) spectroscopy was used for the study of the proposed physical properties. The ODMR method provides the means to identify the surface/interface sites and correlate them with specific optical transition. In addition, this method reveals information about the spin multiplicity of band edge and trapped states and the electron-hole exchange interaction, determines the spectroscopic g-factors, distinguishes between the radiative and nonradiative characteristic of a trapping site, and evaluates the spin-lattice relaxation times.

After providing some background material to establish the interest content of this subject, we summarize the many different ways in which water can be prepared in the amorphous state, making clear that there seems to be more than one distinct amorphous state to be considered. We then give some space to structural and spectroscopic characterization of the distinct states, recognizing that whereas there seems to be unambiguously two distinct states, there may be in fact be more, the additional states mimicking the structures of the higher-density crystalline polymorphs. The low-frequency vibrational properties of the amorphous solid states are then examined in some detail because of the gathering evidence that glassy water, while difficult to form directly from the liquid like other glasses, may have some unusual and almost ideal glassy features, manifested by unusually low states of disorder. This notion is pursued in the following section dealing with thermodynamic and relaxational properties, where the uniquely low excess entropy of the vitreous state of water is confirmed by three different estimates. The fact that the most nearly ideal glass known has no properly established glass transition temperature is highlighted, using known dielectric loss data for amorphous solid water (ASW) and relevant molecular glasses. Finally, the polyamorphism of glassy water, and the kinetic aspects of transformation from one form to the other, are reviewed.

We review recent developments in single-molecule spectroscopy and microscopy. New optical methods provide access to the absorption, emission, or excitation spectra of single nano-objects and can determine either the positions of these objects with subwavelength accuracy or the full three-dimensional orientation of their transition dipole moments. Recent work aims at using single molecules as nanoparts or nanoelements in a variety of molecular-scale devices, from triggered sources of single photons to single-molecular switches. A prominent new direction explores the various interactions between molecules within individual multichromophoric systems obtained by chemical synthesis. These systems are the models for natural self-assembled systems such as the light-harvesting proteins of bacteria and green plants, which are currently studied on a single-molecule basis. Another important class of multichromophoric systems are conjugated polymers. The combination of microscopy with time- and frequency-resolved spectroscopy is opening a wide field of new and exciting applications to individual nano-objects.