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  • Molecules at Solid Surfaces: A Personal Reminiscence
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Gerhard Ertl

    I was fortunate to start my career in physical chemistry at a time when the development of the ultrahigh vacuum technique and of novel physical methods enabled the study of processes on well-defined surfaces at an atomic scale. These investigations included the mechanisms of heterogeneously catalyzed reactions, such as CO oxidation and ammonia synthesis, and phenomena of spatio-temporal self-organization, as described by the concepts of nonlinear dynamics.

    更新日期:2017-06-12
  • From 50 Years Ago, the Birth of Modern Liquid-State Science
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    David Chandler

    The story told in this autobiographical perspective begins 50 years ago, at the 1967 Gordon Research Conference on the Physics and Chemistry of Liquids. It traces developments in liquid-state science from that time, including contributions from the author, and especially in the study of liquid water. It emphasizes the importance of fluctuations and the challenges of far-from-equilibrium phenomena.

    更新日期:2017-06-12
  • Quantum State–Resolved Studies of Chemisorption Reactions
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Helen Chadwick, Rainer D. Beck

    Chemical reactions at the gas–surface interface are ubiquitous in the chemical industry as well as in nature. Investigating these processes at a microscopic, quantum state–resolved level helps develop a predictive understanding of this important class of reactions. In this review, we present an overview of the field of quantum state–resolved gas–surface reactivity measurements that explore the role of the initial quantum state on the dissociative chemisorption of a gas-phase reactant incident on a solid surface. Using molecular beams and either quantum state–specific reactant preparation or product detection by laser excitation, these studies have observed mode specificity and bond selectivity as well as steric effects in chemisorption reactions, highlighting the nonstatistical and complex nature of gas–surface reaction dynamics.

    更新日期:2017-06-12
  • Molecular Photofragmentation Dynamics in the Gas and Condensed Phases
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Michael N.R. Ashfold, Daniel Murdock, Thomas A.A. Oliver

    Exciting a molecule with an ultraviolet photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gas-phase molecule can be viewed as a closed system: Energy and momentum are conserved, and the fragmentation is irreversible. The same is not true in a solution-phase photodissociation process. Solvent interactions may dissipate some of the photoexcitation energy prior to bond fission and will dissipate any excess energy partitioned into the dissociation products. Products that have no analog in the corresponding gas-phase study may arise by, for example, geminate recombination. Here, we illustrate the extent to which dynamical insights from gas-phase studies can inform our understanding of the corresponding solution-phase photochemistry and how, in the specific case of photoinduced ring-opening reactions, solution-phase studies can in some cases reveal dynamical insights more clearly than the corresponding gas-phase study.

    更新日期:2017-06-12
  • Coherent Light Sources at the Nanoscale
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Ankun Yang, Danqing Wang, Weijia Wang, Teri W. Odom

    This review focuses on coherent light sources at the nanoscale, and specifically on lasers exploiting plasmonic cavities that can beat the diffraction limit of light. Conventional lasers exhibit coherent, intense, and directional emission|ԌE|Ԍrger than their operating wavelength. Plasmon lasers show ultrasmall mode confinement, support strong light–matter interactions, and represent a class of devices with extremely small sizes. We discuss the differences between plasmon lasers and traditional ones, and we highlight advances in directionality and tunability through innovative cavity designs and new materials. Challenges and future prospects are also discussed.

    更新日期:2017-06-12
  • Progress Toward a Molecular Mechanism of Water Oxidation in Photosystem II
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    David J. Vinyard, Gary W. Brudvig

    The active site of photosynthetic water oxidation is the oxygen-evolving complex (OEC) in the photosystem II (PSII) reaction center. The OEC is a Mn4CaO5 cluster embedded in the PSII protein matrix, and it cycles through redox intermediates known as Si states (i = 0–4). Significant progress has been made in understanding the inorganic and physical chemistry of states S0–S3 through experiment and theory. The chemical steps from S3 to S0 are more poorly understood, however, because the identity of the substrate water molecules and the mechanism of O–O bond formation are not well established. In this review, we highlight both the consensuses and the remaining challenges of PSII research.

    更新日期:2017-06-12
  • Computer Simulations of Intrinsically Disordered Proteins
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Song-Ho Chong, Prathit Chatterjee, Sihyun Ham

    The investigation of intrinsically disordered proteins (IDPs) is a new frontier in structural and molecular biology that requires a new paradigm to connect structural disorder to function. Molecular dynamics simulations and statistical thermodynamics potentially offer ideal tools for atomic-level characterizations and thermodynamic descriptions of this fascinating class of proteins that will complement experimental studies. However, IDPs display sensitivity to inaccuracies in the underlying molecular mechanics force fields. Thus, achieving an accurate structural characterization of IDPs via simulations is a challenge. It is also daunting to perform a configuration-space integration over heterogeneous structural ensembles sampled by IDPs to extract, in particular, protein configurational entropy. In this review, we summarize recent efforts devoted to the development of force fields and the critical evaluations of their performance when applied to IDPs. We also survey recent advances in computational methods for protein configurational entropy that aim to provide a thermodynamic link between structural disorder and protein activity.

    更新日期:2017-06-12
  • QM/MM Geometry Optimization on Extensive Free-Energy Surfaces for Examination of Enzymatic Reactions and Design of Novel Functional Properties of Proteins
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Shigehiko Hayashi, Yoshihiro Uchida, Taisuke Hasegawa, Masahiro Higashi, Takahiro Kosugi, Motoshi Kamiya

    Many remarkable molecular functions of proteins use their characteristic global and slow conformational dynamics through coupling of local chemical states in reaction centers with global conformational changes of proteins. To theoretically examine the functional processes of proteins in atomic detail, a methodology of quantum mechanical/molecular mechanical (QM/MM) free-energy geometry optimization is introduced. In the methodology, a geometry optimization of a local reaction center is performed with a quantum mechanical calculation on a free-energy surface constructed with conformational samples of the surrounding protein environment obtained by a molecular dynamics simulation with a molecular mechanics force field. Geometry optimizations on extensive free-energy surfaces by a QM/MM reweighting free-energy self-consistent field method designed to be variationally consistent and computationally efficient have enabled examinations of the multiscale molecular coupling of local chemical states with global protein conformational changes in functional processes and analysis and design of protein mutants with novel functional properties.

    更新日期:2017-06-12
  • Development of New Density Functional Approximations
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Neil Qiang Su, Xin Xu

    Kohn–Sham density functional theory has become the leading electronic structure method for atoms, molecules, and extended systems. It is in principle exact, but any practical application must rely on density functional approximations (DFAs) for the exchange-correlation energy. Here we emphasize four aspects of the subject: (a) philosophies and strategies for developing DFAs; (b) classification of DFAs; (c) major sources of error in existing DFAs; and (d) some recent developments and future directions.

    更新日期:2017-06-12
  • Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Craig A. Taatjes

    The carbonyl oxide intermediates in the ozonolysis of alkenes, often known as Criegee intermediates, are potentially important reactants in Earth's atmosphere. For decades, careful analysis of ozonolysis systems was employed to derive an understanding of the formation and reactions of these species. Recently it has proved possible to synthesize at least some of these intermediates separately from ozonolysis, and hence to measure their reaction kinetics directly. Direct measurements have allowed new or more detailed understanding of each type of gas-phase reaction that carbonyl oxides undergo, often acting as a complement to highly detailed ozonolysis experiments. Moreover, the use of direct characterization methods to validate increasingly accurate theoretical investigations can enhance their impact well beyond the set of specific reactions that have been measured. Reactions that initiate particles or fuel their growth could be a new frontier for direct measurements of Criegee intermediate chemistry.

    更新日期:2017-06-12
  • Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Miao Zhang, Heinz Frei

    Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. Combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

    更新日期:2017-06-12
  • Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    David L. Osborn

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

    更新日期:2017-06-12
  • Phospholipid Bilayers: Stability and Encapsulation of Nanoparticles
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Elnaz Alipour, Duncan Halverson, Samantha McWhirter, Gilbert C. Walker

    Nanoparticles are widely studied for their potential medical uses in diagnostics and therapeutics. The interface between a nanoparticle and its target has been a focus of research, both to guide the nanoparticle and to prevent it from deactivating. Given nature's frequent use of phospholipid vesicles as carriers, much attention has been paid to phospholipids as a vehicle for drug delivery.

    更新日期:2017-06-12
  • Ice Surfaces
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Mary Jane Shultz

    Ice is a fundamental solid with important environmental, biological, geological, and extraterrestrial impact. The stable form of ice at atmospheric pressure is hexagonal ice, Ih. Despite its prevalence, Ih remains an enigmatic solid, in part due to challenges in preparing samples for fundamental studies. Surfaces of ice present even greater challenges. Recently developed methods for preparation of large single-crystal samples make it possible to reproducibly prepare any chosen face to address numerous fundamental questions. This review describes preparation methods along with results that firmly establish the connection between the macroscopic structure (observed in snowflakes, microcrystallites, or etch pits) and the molecular-level configuration (detected with X-ray or electron scattering techniques). Selected results of probing interactions at the ice surface, including growth from the melt, surface vibrations, and characterization of the quasi-liquid layer, are discussed.

    更新日期:2017-06-12
  • Metal-Free Motifs for Solar Fuel Applications
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Stefan Ilic, Marija R. Zoric, Usha Pandey Kadel, Yunjing Huang, Ksenija D. Glusac

    Metal-free motifs, such as graphitic carbon nitride, conjugated polymers, and doped nanostructures, are emerging as a new class of Earth-abundant materials for solar fuel devices. Although these metal-free structures show great potential, detailed mechanistic understanding of their performance remains limited. Here, we review important experimental and theoretical findings relevant to the role of metal-free motifs as either photoelectrodes or electrocatalysts. First, the light-harvesting characteristics of metal-free photoelectrodes (band energetics, exciton binding energies, charge carrier mobilities and lifetimes) are discussed and contrasted with those in traditional inorganic semiconductors (such as Si). Second, the mechanistic insights into the electrocatalytic oxygen reduction and evolution reactions, hydrogen evolution reaction, and carbon dioxide reduction reaction by metal-free motifs are summarized, including experimental surface-sensitive spectroscopy findings, studies on small molecular models, and computational modeling of these chemical transformations.

    更新日期:2017-06-12
  • Ion–Molecule Reaction Dynamics
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Jennifer Meyer, Roland Wester

    We review the recent advances in the investigation of the dynamics of ion–molecule reactions. During the past decade, the combination of single-collision experiments in crossed ion and neutral beams with the velocity map ion imaging detection technique has enabled a wealth of studies on ion–molecule reactions. These methods, in combination with chemical dynamics simulations, have uncovered new and unexpected reaction mechanisms, such as the roundabout mechanism and the subtle influence of the leaving group in anion–molecule nucleophilic substitution reactions. For this important class of reactions, as well as for many fundamental cation–molecule reactions, the information obtained with crossed-beam imaging is discussed. The first steps toward understanding micro-solvation of ion–molecule reaction dynamics are presented. We conclude with the presentation of several interesting directions for future research.

    更新日期:2017-06-12
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  • Computational Analysis of Vibrational Sum Frequency Generation Spectroscopy
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Tatsuya Ishiyama, Akihiro Morita

    Vibrational sum frequency generation (VSFG) spectroscopy is a widely used probe of interfaces and, having ideal surface sensitivity and selectivity, is particularly powerful when applied to wet and soft interfaces. Although VSFG spectroscopy can sensitively detect molecular details of interfaces, interpretation of observed spectra has, until recently, been challenging and often ambiguous. The situation has been greatly improved by remarkable advances in computational VSFG analysis on the basis of molecular modeling and molecular dynamics simulation. This article reviews the basic idea of computational VSFG analysis and recent applications to both aqueous and organic interfaces.

    更新日期:2017-06-12
  • Hot Charge Carrier Transmission from Plasmonic Nanostructures
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Phillip Christopher, Martin Moskovits

    Surface plasmons have recently been harnessed to carry out processes such as photovoltaic current generation, redox photochemistry, photocatalysis, and photodetection, all of which are enabled by separating energetic (hot) electrons and holes—processes that, previously, were the domain of semiconductor junctions. Currently, the power conversion efficiencies of systems using plasmon excitation are low. However, the very large electron/hole per photon quantum efficiencies observed for plasmonic devices fan the hope of future improvements through a deeper understanding of the processes involved and through better device engineering, especially of critical interfaces such as those between metallic and semiconducting nanophases (or adsorbed molecules). In this review, we focus on the physics and dynamics governing plasmon-derived hot charge carrier transfer across, and the electronic structure at, metal–semiconductor (molecule) interfaces, where we feel the barriers contributing to low efficiencies reside. We suggest some areas of opportunity that deserve early attention in the still-evolving field of hot carrier transmission from plasmonic nanostructures to neighboring phases.

    更新日期:2017-06-12
  • Calculating Natural Optical Activity of Molecules from First Principles
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Monika Srebro-Hooper, Jochen Autschbach

    Computations of natural optical activity (OA) from first principles (ab initio) have become indispensable in chiroptical studies of molecular systems. Calculations are used to assign absolute configurations and to analyze chiroptical data, providing a basis for understanding their origin as well as for assigning and predicting experimental results. In this article, methodology for OA computations is outlined and accompanied by a review of selected, mainly recent (ca. 2010–2016) achievements in optical rotation, electronic and vibrational circular dichroism, and Raman OA calculations. We discuss some important aspects of the computational models and methodological developments, along with recently proposed approaches to analyze and interpret OA parameters. We highlight applications of chiroptical computational methods in studies of helicenes and chiral nanoparticles.

    更新日期:2017-06-12
  • Random-Phase Approximation Methods
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Guo P. Chen, Vamsee K. Voora, Matthew M. Agee, Sree Ganesh Balasubramani, Filipp Furche

    Random-phase approximation (RPA) methods are rapidly emerging as cost-effective validation tools for semilocal density functional computations. We present the theoretical background of RPA in an intuitive rather than formal fashion, focusing on the physical picture of screening and simple diagrammatic analysis. A new decomposition of the RPA correlation energy into plasmonic modes leads to an appealing visualization of electron correlation in terms of charge density fluctuations. Recent developments in the areas of beyond-RPA methods, RPA correlation potentials, and efficient algorithms for RPA energy and property calculations are reviewed. The ability of RPA to approximately capture static correlation in molecules is quantified by an analysis of RPA natural occupation numbers. We illustrate the use of RPA methods in applications to small-gap systems such as open-shell d- and f-element compounds, radicals, and weakly bound complexes, where semilocal density functional results exhibit strong functional dependence.

    更新日期:2017-06-12
  • The Hydrated Electron
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    John M. Herbert, Marc P. Coons

    Existence of a hydrated electron as a byproduct of water radiolysis was established more than 50 years ago, yet this species continues to attract significant attention due to its role in radiation chemistry, including DNA damage, and because questions persist regarding its detailed structure. This work provides an overview of what is known in regards to the structure and spectroscopy of the hydrated electron, both in liquid water and in clusters , the latter of which provide model systems for how water networks accommodate an excess electron. In clusters, the existence of both surface-bound and internally bound states of the excess electron has elicited much debate, whereas in bulk water there are questions regarding how best to understand the structure of the excess electron's spin density. The energetics of the equilibrium species e−(aq) and its excited states, in bulk water and at the air/water interface, are also addressed.

    更新日期:2017-06-12
  • Ultrafast X-Ray Crystallography and Liquidography
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Hosung Ki, Key Young Oang, Jeongho Kim, Hyotcherl Ihee

    Time-resolved X-ray diffraction provides direct information on three-dimensional structures of reacting molecules and thus can be used to elucidate structural dynamics of chemical and biological reactions. In this review, we discuss time-resolved X-ray diffraction on small molecules and proteins with particular emphasis on its application to crystalline (crystallography) and liquid-solution (liquidography) samples. Time-resolved X-ray diffraction has been used to study picosecond and slower dynamics at synchrotrons and can now access even femtosecond dynamics with the recent arrival of X-ray free-electron lasers.

    更新日期:2017-06-12
  • Roaming: A Phase Space Perspective
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Frédéric A.L. Mauguière, Peter Collins, Zeb C. Kramer, Barry K. Carpenter, Gregory S. Ezra, Stavros C. Farantos, Stephen Wiggins

    In this review we discuss the recently described roaming mechanism for chemical reactions from the point of view of nonlinear dynamical systems in phase space. The recognition of the roaming phenomenon shows the need for further developments in our fundamental understanding of basic reaction dynamics, as is made clear by considering some questions that cut across most studies of roaming: Is the dynamics statistical? Can transition state theory be applied to estimate roaming reaction rates? What role do saddle points on the potential energy surface play in explaining the behavior of roaming trajectories? How do we construct a dividing surface that is appropriate for describing the transformation from reactants to products for roaming trajectories? How should we define the roaming region? We show that the phase space perspective on reaction dynamics provides the setting in which these questions can be properly framed and answered. We illustrate these ideas by considering photodissociation of formaldehyde. The phase-space formulation allows an unambiguous description of all possible reactive events, which also allows us to uncover the phase space mechanism that explains which trajectories roam, as opposed to evolving toward a different reactive event.

    更新日期:2017-06-12
  • Extending Quantum Chemistry of Bound States to Electronic Resonances
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Thomas-C. Jagau, Ksenia B. Bravaya, Anna I. Krylov

    Electronic resonances are metastable states with finite lifetime embedded in the ionization or detachment continuum. They are ubiquitous in chemistry, physics, and biology. Resonances play a central role in processes as diverse as DNA radiolysis, plasmonic catalysis, and attosecond spectroscopy. This review describes novel equation-of-motion coupled-cluster (EOM-CC) methods designed to treat resonances and bound states on an equal footing. Built on complex-variable techniques such as complex scaling and complex absorbing potentials that allow resonances to be associated with a single eigenstate of the molecular Hamiltonian rather than several continuum eigenstates, these methods extend electronic-structure tools developed for bound states to electronic resonances. Selected examples emphasize the formal advantages as well as the numerical accuracy of EOM-CC in the treatment of electronic resonances. Connections to experimental observables such as spectra and cross sections, as well as practical aspects of implementing complex-valued approaches, are also discussed.

    更新日期:2017-06-12
  • The Importance of Being Inconsistent
    Annu. Rev. Phys. Chem. (IF 14.741) Pub Date : 2017-05-02
    Adam Wasserman, Jonathan Nafziger, Kaili Jiang, Min-Cheol Kim, Eunji Sim, Kieron Burke

    We review the role of self-consistency in density functional theory (DFT). We apply a recent analysis to both Kohn–Sham and orbital-free DFT, as well as to partition DFT, which generalizes all aspects of standard DFT. In each case, the analysis distinguishes between errors in approximate functionals versus errors in the self-consistent density. This yields insights into the origins of many errors in DFT calculations, especially those often attributed to self-interaction or delocalization error. In many classes of problems, errors can be substantially reduced by using better densities. We review the history of these approaches, discuss many of their applications, and give simple pedagogical examples.

    更新日期:2017-06-12
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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