Annual Review of Physical Chemistry - Volume 53, 2002

Linear optical spectroscopies have long been used to study the behavior of liquids. Laser technology has progressed to the point that it has become possible to perform nonlinear optical experiments that probe higher-order correlation functions in liquids, opening a new window into our understanding of the microscopic details of solution-phase processes. Here we review advances that have been made in recent years in employing higher-order electronic and vibrational spectroscopies to study liquid-state dynamics and structure.

The use of photoelectron angular distributions (PADs) as a probe in short-pulse, pump-probe scenarios is reviewed. We focus on concepts, on the insight that can be gained through theoretical analysis, on applications, and on future opportunities. Time-resolved PADs are sensitive to both the time-evolving rotational composition of wavepackets and their time-evolving electronic symmetry. The former feature renders this observable a potential probe of molecular structure, intensity effects, and rotational perturbations. The latter feature renders the PAD a potential probe of radiationless transitions.

Recent studies of state-resolved angular distributions show the participation of reactive scattering resonances in the simplest chemical reaction. This review is intended for those who wish to learn about the state-of-the-art in the study of the H + H2 reaction family that has made this breakthrough possible. This review is also intended for those who wish to gain insight into the nature of reactive scattering resonances. Following a tour across several fields of physics and chemistry where the concept of resonance has been crucial for the understanding of new phenomena, we offer an operational definition and taxonomy of reactive scattering resonances. We introduce simple intuitive models to illustrate each resonance type. We focus next on the last decade of H + H2 reaction dynamics. Emphasis is placed on the various experimental approaches that have been applied to the search for resonance behavior in the H + H2 reaction family. We conclude by sketching the road ahead in the study of H + H2 reactive scattering resonances.

The recent developments of vacuum ultraviolet (VUV) laser and third generation synchrotron radiation sources, together with the introduction of pulsed field ionization (PFI) schemes for photoion-photoelectron detection, have had a profound impact on the field of VUV spectroscopy and chemistry. Owing to the mediation of near-resonant autoionizing states, rovibronic states of ions with negligible Franck-Condon factors for direct photoionization can be examined by VUV-PFI measurements with rotational resolutions. The VUV-PFI spectra thus obtained have provided definitive ionization energies (IEs) for many small molecules. The recent synchrotron-based PFI-photoelectron-photoion coincidence experiments have demonstrated that dissociative photoionization thresholds for a range of molecules can be determined to the same precision as in PFI-photoelectron measurements. Combining appropriate dissociation thresholds and IEs measured in PFI studies, thermochemical data for many neutrals and cations can be determined with unprecedented precision. The further development of two-color excitation-ionization schemes promises to expand the scope of spectroscopic and chemical applications using the photoionization-photoelectron method.

The molecular Hamiltonian represents one of the most basic concepts in spectroscopy and molecular reaction dynamics. Its derivation is notoriously difficult owing to the use of a rotating reference frame which, in turn, is necessary to define the concept of vibration and rotation. In this article, we review the construction of the molecular Hamiltonian in normal mode and in internal coordinates. For normal mode coordinates, the Watson Hamiltonian including its modification for linear molecules is derived using an approach based on classical mechanics and the Podolsky transformation. The method is subsequently used to derive the molecular Hamiltonian in terms of Jacobi and valence coordinates. Results are presented for the triatomic system and for the extension toward N-atom systems with N ≥ 3.

The aggregation of monomers into polymers, whether by covalent or noncovalent interactions, is often reversible and frequently occurs with the entropy and enthalpy of the aggregation sharing the same sign. In such a case, the aggregation goes forward or reverses, depending on such variables as temperature and composition, rather like a phase transition. We explore the physical chemistry of three such systems: an organic monomer (α-methylstyrene), an inorganic monomer (sulfur), and a biopolymer (actin). We compare the available theories and experiments and list issues still open.

Recent developments in scanning tunneling microscopy studies of the electronic properties of single-walled carbon nanotubes are reviewed. A broad range of topics focused on the unique electronic properties of nanotubes are discussed, including (a) the underlying theoretical description of the electronic properties of nanotubes; (b) the roles of finite curvature and broken symmetries in perturbing electronic properties; (c) the unique one-dimensional energy dispersion in nanotubes; (d) the nature of end states; (e) quantum size effects in short tubes; (f) the interactions between local spins and carriers in metallic systems (the Kondo effect); and (g) the atomic structure and electronic properties of intramolecular junctions. The implications of these studies for understanding fundamental one-dimensional physics and future nanotube device applications are discussed.

Electron transfer between a molecular resonance and a metal surface is a ubiquitous process in many chemical disciplines, ranging from molecular electronics to surface photochemistry. This problem has been probed recently by two-photon photoemission spectroscopy. The first photon excites an electron from an occupied metal state to an unoccupied molecular resonance. Subsequent evolution of the excited electronic wavefunction is probed in energy, momentum, and time domains by the absorption of a second photon, which ionizes the electron for detection. These experiments reveal the important roles of molecule-metal wavefunction mixing, intermolecular band formation, polarization, and localization in interfacial electron transfer.

Recent applications of density functional theory base ab initio molecular dynamics in chemical relevant systems are reviewed. The emphasis is on the dynamical aspect in the study of structures, reaction mechanisms, and electronic properties in both the molecular and condensed phases. Examples were chosen from fluxional molecules, solution reactions, and biological systems to illustrate the broad potential applications and unique information that can be obtained from ab initio molecular dynamics calculations. Recent advances in the development of efficient numerical algorithms for the prediction of spectroscopic properties are highlighted.

This article reviews the concepts and methods of transition path sampling. These methods allow computational studies of rare events without requiring prior knowledge of mechanisms, reaction coordinates, and transition states. Based upon a statistical mechanics of trajectory space, they provide a perspective with which time dependent phenomena, even for systems driven far from equilibrium, can be examined with the same types of importance sampling tools that in the past have been applied so successfully to static equilibrium properties.

The powerful computational resources available to scientists today, together with recent improvements in electronic structure calculation algorithms, are providing important new tools for researchers in the fields of surface science and catalysis. In this review, we discuss first principles calculations that are now capable of providing qualitative and, in many cases, quantitative insights into surface chemistry. The calculations can aid in the establishment of chemisorption trends across the transition metals, in the characterization of reaction pathways on individual metals, and in the design of novel catalysts. First principles studies provide an excellent fundamental complement to experimental investigations of the above phenomena and can often allow the elucidation of important mechanistic details that would be difficult, if not impossible, to determine from experiments alone.

This chapter discusses recent progress in the investigation and use of ¹³C, ¹⁵N, and ¹⁹F nuclear magnetic resonance (NMR) chemical shifts and chemical shift tensors in proteins and model systems primarily using quantum chemical (ab initio Hartree-Fock and density functional theory) techniques. Correlations between spectra and structure are made and the techniques applied to other spectroscopic and electrostatic properties as well, including hydrogen bonding, ligand binding to heme proteins, J-couplings, electric field gradients, and atoms-in-molecules theory, together with a brief review of the use of NMR chemical shifts in drug design.

Recent experimental advances have uncovered many of the diverse reaction pathways following an energetic collision between a molecular ion and a solid surface. Hyperthermal translational energies (5–500 eV) are sufficient to activate a number of chemical transformations in the near-surface region, including charge transfer, dissociation, abstraction, and deposition. State-of-the-art scattering studies probe the consumption and disposal of energy and the effects of approach geometry and surface electronic structure on the operative reaction mechanisms. These fundamental investigations provide insight relevant to the fabrication of microelectronics devices, the interaction of space vehicles with the earth's atmosphere, and the development of analytical techniques in mass spectrometry.

This paper reviews the molecular theory of hydrophobic effects relevant to biomolecular structure and assembly in aqueous solution. Recent progress has resulted in simple, validated molecular statistical thermodynamic theories and clarification of confusing theories of decades ago. Current work is resolving effects of wider variations of thermodynamic state, e.g., pressure denaturation of soluble proteins, and more exotic questions such as effects of surface chemistry in treating stability of macromolecular structures in aqueous solution.

Recently, sum frequency generation (SFG) vibrational spectroscopy has been developed into a powerful technique to study surfaces of polymer materials. This review summarizes the significant achievements in understanding surface molecular chemical structures of polymer materials obtained by SFG. It reviews in situ detection at the molecular level of surface structures of some common polymers in air, surface segregation of small end groups, polymer surface restructuring in water, and step-wise changed polymer blend surfaces. Studies of surface glass transition and surface structures modified by rubbing, plasma deposition, UV light irradiation, oxygen ion and radical irradiation, and wet etching are also discussed. SFG probing of polymer surfaces provides valuable insights into the relations between polymer surface structures and surface properties, which will assist in the design of polymer materials with desired surface properties.

This review discusses methods for the incorporation of quantum mechanical effects into enzyme kinetics simulations in which the enzyme is an explicit part of the model. We emphasize three aspects: (a) use of quantum mechanical electronic structure methods such as molecular orbital theory and density functional theory, usually in conjunction with molecular mechanics; (b) treating vibrational motions quantum mechanically, either in an instantaneous harmonic approximation, or by path integrals, or by a three-dimensional wave function coupled to classical nuclear motion; (c) incorporation of multidimensional tunneling approximations into reaction rate calculations.

This review presents a case study of the direct, real-time observation of a surface photochemical reaction, namely the frustrated photodesorption of alkali atoms from noble metal surfaces. Charge transfer excitation of an electron from the metal substrate into an unoccupied resonance of the alkali atom instantaneously turns on the repulsive Coulomb force inducing the nuclear motion of both the adsorbate and substrate atoms. The incipient nuclear wave packet dynamics are documented for the case of Cs/Cu(111) through the accompanying change in the surface electronic structure. The intimate view of atoms attempting to escape the surface bond highlights the unique role of the substrate in the electronic and nuclear dynamics that ultimately determine the product yields. Moreover, slow dephasing of the coherent polarization is exploited to demonstrate the control of nuclear wave packets through the phase of the excitation light.

This article reviews a new and general theory of nonuniform fluids that naturally incorporates molecular scale information into the classical van der Waals theory of slowly varying interfaces. The method optimally combines two standard approximations, molecular (mean) field theory to describe interface formation and linear response (or Gaussian fluctuation) theory to describe local structure. Accurate results have been found in many different applications in nonuniform simple fluids and these ideas may have important implications for the theory of hydrophobic interactions in water.