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  • Addressing the Challenge of Molecular Change: An Interim Report
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Raphael D. Levine

    Invited by the editorial committee of the Annual Review of Physical Chemistry to “contribute my autobiography,” I present it here, as I understand the term. It is about my parents, my mentors, my coworkers, and my friends in learning and the scientific problems that we tried to address. Courtesy of the editorial assistance of Annual Reviews, some of the science is in the figure captions and sidebars. I am by no means done: I am currently trying to fuse the quantitative rigor of physical chemistry with systems biology while also dealing with a post–Born-Oppenheimer regime in electronic dynamics and am attempting to instruct molecules to perform advanced logic.

    更新日期:2018-07-14
  • Biomimetic Structural Materials: Inspiration from Design and Assembly
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Nicholas A. Yaraghi, David Kisailus

    Nature assembles weak organic and inorganic constituents into sophisticated hierarchical structures, forming structural composites that demonstrate impressive combinations of strength and toughness. Two such composites are the nacre structure forming the inner layer of many mollusk shells, whose brick-and-mortar architecture has been the gold standard for biomimetic composites, and the cuticle forming the arthropod exoskeleton, whose helicoidal fiber-reinforced architecture has only recently attracted interest for structural biomimetics. In this review, we detail recent biomimetic efforts for the fabrication of strong and tough composite materials possessing the brick-and-mortar and helicoidal architectures. Techniques discussed for the fabrication of nacre- and cuticle-mimetic structures include freeze casting, layer-by-layer deposition, spray deposition, magnetically assisted slip casting, fiber-reinforced composite processing, additive manufacturing, and cholesteric self-assembly. Advantages and limitations to these processes are discussed, as well as the future outlook on the biomimetic landscape for structural composite materials.

    更新日期:2018-07-14
  • An Active Approach to Colloidal Self-Assembly
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Stewart A. Mallory, Chantal Valeriani, Angelo Cacciuto

    In this review, we discuss recent advances in the self-assembly of self-propelled colloidal particles and highlight some of the most exciting results in this field, with a specific focus on dry active matter. We explore this phenomenology through the lens of the complexity of the colloidal building blocks. We begin by considering the behavior of isotropic spherical particles. We then discuss the case of amphiphilic and dipolar Janus particles. Finally, we show how the geometry of the colloids and/or the directionality of their interactions can be used to control the physical properties of the assembled active aggregates, and we suggest possible strategies for how to exploit activity as a tunable driving force for self-assembly. The unique properties of active colloids lend promise to the design of the next generation of functional, environment-sensing microstructures able to perform specific tasks in an autonomous and targeted manner.

    更新日期:2018-07-14
  • Excitons in Single-Walled Carbon Nanotubes and Their Dynamics
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Amanda R. Amori, Zhentao Hou, Todd D. Krauss

    Understanding exciton dynamics in single-walled carbon nanotubes (SWCNTs) is essential to unlocking the many potential applications of these materials. This review summarizes recent progress in understanding exciton photophysics and, in particular, exciton dynamics in SWCNTs. We outline the basic physical and electronic properties of SWCNTs, as well as bright and dark transitions within the framework of a strongly bound one-dimensional excitonic model. We discuss the many facets of ultrafast carrier dynamics in SWCNTs, including both single-exciton states (bright and dark) and multiple-exciton states. Photophysical properties that directly relate to excitons and their dynamics, including exciton diffusion lengths, chemical and structural defects, environmental effects, and photoluminescence photon statistics as observed through photon antibunching measurements, are also discussed. Finally, we identify a few key areas for advancing further research in the field of SWCNT excitons and photonics.

    更新日期:2018-07-14
  • Slow Photoelectron Velocity-Map Imaging of Cryogenically Cooled Anions
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Marissa L. Weichman, Daniel M. Neumark

    Slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled anions (cryo-SEVI) is a powerful technique for elucidating the vibrational and electronic structure of neutral radicals, clusters, and reaction transition states. SEVI is a high-resolution variant of anion photoelectron spectroscopy based on photoelectron imaging that yields spectra with energy resolution as high as 1–2 cm−1. The preparation of cryogenically cold anions largely eliminates hot bands and dramatically narrows the rotational envelopes of spectral features, enabling the acquisition of well-resolved photoelectron spectra for complex and spectroscopically challenging species. We review the basis and history of the SEVI method, including recent experimental developments that have improved its resolution and versatility. We then survey recent SEVI studies to demonstrate the utility of this technique in the spectroscopy of aromatic radicals, metal and metal oxide clusters, nonadiabatic interactions between excited states of small molecules, and transition states of benchmark bimolecular reactions.

    更新日期:2018-07-14
  • Graph Theory and Ion and Molecular Aggregation in Aqueous Solutions
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Jun-Ho Choi, Hochan Lee, Hyung Ran Choi, Minhaeng Cho

    In molecular and cellular biology, dissolved ions and molecules have decisive effects on chemical and biological reactions, conformational stabilities, and functions of small to large biomolecules. Despite major efforts, the current state of understanding of the effects of specific ions, osmolytes, and bioprotecting sugars on the structure and dynamics of water H-bonding networks and proteins is not yet satisfactory. Recently, to gain deeper insight into this subject, we studied various aggregation processes of ions and molecules in high-concentration salt, osmolyte, and sugar solutions with time-resolved vibrational spectroscopy and molecular dynamics simulation methods. It turns out that ions (or solute molecules) have a strong propensity to self-assemble into large and polydisperse aggregates that affect both local and long-range water H-bonding structures. In particular, we have shown that graph-theoretical approaches can be used to elucidate morphological characteristics of large aggregates in various aqueous salt, osmolyte, and sugar solutions. When ion and molecular aggregates in such aqueous solutions are treated as graphs, a variety of graph-theoretical properties, such as graph spectrum, degree distribution, clustering coefficient, minimum path length, and graph entropy, can be directly calculated by considering an ensemble of configurations taken from molecular dynamics trajectories. Here we show percolating behavior exhibited by ion and molecular aggregates upon increase in solute concentration in high solute concentrations and discuss compelling evidence of the isomorphic relation between percolation transitions of ion and molecular aggregates and water H-bonding networks. We anticipate that the combination of graph theory and molecular dynamics simulation methods will be of exceptional use in achieving a deeper understanding of the fundamental physical chemistry of dissolution and in describing the interplay between the self-aggregation of solute molecules and the structure and dynamics of water.

    更新日期:2018-07-14
  • Permutationally Invariant Potential Energy Surfaces
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Chen Qu, Qi Yu, Joel M. Bowman

    Over the past decade, about 50 potential energy surfaces (PESs) for polyatomics with 4–11 atoms and for clusters have been calculated using the permutationally invariant polynomial method. This is a general, mainly linear least-squares method for precise mathematical fitting of tens of thousands of electronic energies for reactive and nonreactive systems. A brief tutorial of the methodology is given, including several recent improvements. Recent applications to the formic acid dimer (the current record holder in size for a reactive system), the H2-H2O complex, and four protonated water clusters [H+(H2O)n=2,3,4,6] are given. The last application also illustrates extension to large clusters using the many-body representation.

    更新日期:2018-07-14
  • Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    António J.C. Varandas

    Because the one-electron basis set limit is difficult to reach in correlated post-Hartree–Fock ab initio calculations, the low-cost route of using methods that extrapolate to the estimated basis set limit attracts immediate interest. The situation is somewhat more satisfactory at the Hartree–Fock level because numerical calculation of the energy is often affordable at nearly converged basis set levels. Still, extrapolation schemes for the Hartree–Fock energy are addressed here, although the focus is on the more slowly convergent and computationally demanding correlation energy. Because they are frequently based on the gold-standard coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)], correlated calculations are often affordable only with the smallest basis sets, and hence single-level extrapolations from one raw energy could attain maximum usefulness. This possibility is examined. Whenever possible, this review uses raw data from second-order Møller–Plesset perturbation theory, as well as CCSD, CCSD(T), and multireference configuration interaction methods. Inescapably, the emphasis is on work done by the author's research group. Certain issues in need of further research or review are pinpointed.

    更新日期:2018-07-14
  • Connections Between Theory and Experiment for Gold and Silver Nanoclusters
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    K.L. Dimuthu M. Weerawardene, Hannu Häkkinen, Christine M. Aikens

    Ligand-stabilized gold and silver nanoparticles are of tremendous current interest in sensing, catalysis, and energy applications. Experimental and theoretical studies have closely interacted to elucidate properties such as the geometric and electronic structures of these fascinating systems. In this review, the interplay between theory and experiment is described; areas such as optical absorption and doping, where the theory–experiment connections are well established, are discussed in detail; and the current status of these connections in newer fields of study, such as luminescence, transient absorption, and the effects of solvent and the surrounding environment, are highlighted. Close communication between theory and experiment has been extremely valuable for developing an understanding of these nanocluster systems in the past decade and will undoubtedly continue to play a major role in future years.

    更新日期:2018-07-14
  • Characterization of Intermediate Oxidation States in CO2 Activation
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Leah G. Dodson, Michael C. Thompson, J. Mathias Weber

    Redox chemistry during the activation of carbon dioxide involves changing the charge state in a CO2 molecular unit. However, such changes are usually not well described by integer formal charges, and one can think of COO functional units as being in intermediate oxidation states. In this article, we discuss the properties of CO2 and CO2-based functional units in various charge states. Besides covering isolated CO2 and its ions, we describe the CO2-based ionic species formate, oxalate, and carbonate. Finally, we provide an overview of CO2-based functional groups and ligands in clusters and metal–organic complexes.

    更新日期:2018-07-14
  • Measuring Electric Fields in Biological Matter Using the Vibrational Stark Effect of Nitrile Probes
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2016-06-09
    Joshua D. Slocum, Lauren J. Webb

    Measurement of the electrostatic interactions that give rise to biological functions has been a longstanding challenge in biophysics. Advances in spectroscopic techniques over the past two decades have allowed for the direct measurement of electric fields in a wide variety of biological molecules and systems via the vibrational Stark effect (VSE). The frequency of the nitrile stretching oscillation has received much attention as an electric field reporter because of its sensitivity to electric fields and its occurrence in a relatively transparent region of the infrared spectrum. Despite these advantages and its wide use as a VSE probe, the nitrile stretching frequency is sensitive to hydrogen bonding in a way that complicates the straightforward relationship between measured frequency and environmental electric field. Here we highlight recent applications of nitrile VSE probes with an emphasis on experiments that have helped shape our understanding of the determinants of nitrile frequencies in both hydrogen bonding and nonhydrogen bonding environments.

    更新日期:2018-07-14
  • Chemical Kinetics for Bridging Molecular Mechanisms and Macroscopic Measurements of Amyloid Fibril Formation
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Thomas C.T. Michaels, Anđela Šarić, Johnny Habchi, Sean Chia, Georg Meisl, Michele Vendruscolo, Christopher M. Dobson, Tuomas P.J. Knowles

    Understanding how normally soluble peptides and proteins aggregate to form amyloid fibrils is central to many areas of modern biomolecular science, ranging from the development of functional biomaterials to the design of rational therapeutic strategies against increasingly prevalent medical conditions such as Alzheimer's and Parkinson's diseases. As such, there is a great need to develop models to mechanistically describe how amyloid fibrils are formed from precursor peptides and proteins. Here we review and discuss how ideas and concepts from chemical reaction kinetics can help to achieve this objective. In particular, we show how a combination of theory, experiments, and computer simulations, based on chemical kinetics, provides a general formalism for uncovering, at the molecular level, the mechanistic steps that underlie the phenomenon of amyloid fibril formation.

    更新日期:2018-07-14
  • Electronic Transport in Two-Dimensional Materials
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Vinod K. Sangwan, Mark C. Hersam

    Two-dimensional (2D) materials have captured the attention of the scientific community due to the wide range of unique properties at nanometer-scale thicknesses. While significant exploratory research in 2D materials has been achieved, the understanding of 2D electronic transport and carrier dynamics remains in a nascent stage. Furthermore, because prior review articles have provided general overviews of 2D materials or specifically focused on charge transport in graphene, here we instead highlight charge transport mechanisms in post-graphene 2D materials, with particular emphasis on transition metal dichalcogenides and black phosphorus. For these systems, we delineate the intricacies of electronic transport, including band structure control with thickness and external fields, valley polarization, scattering mechanisms, electrical contacts, and doping. In addition, electronic interactions between 2D materials are considered in the form of van der Waals heterojunctions and composite films. This review concludes with a perspective on the most promising future directions in this fast-evolving field.

    更新日期:2018-07-14
  • Vibrational and Nonadiabatic Coherence in 2D Electronic Spectroscopy, the Jahn–Teller Effect, and Energy Transfer
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2016-06-09
    David M. Jonas

    Femtosecond two-dimensional (2D) Fourier transform spectroscopy generates and probes several types of coherence that characterize the couplings between vibrational and electronic motions. These couplings have been studied in molecules with Jahn–Teller conical intersections, pseudo-Jahn–Teller funnels, dimers, molecular aggregates, photosynthetic light harvesting complexes, and photosynthetic reaction centers. All have closely related Hamiltonians and at least two types of vibrations, including one that is decoupled from the electronic dynamics and one that is nonadiabatically coupled. Polarized pulse sequences can often be used to distinguish these types of vibrations. Electronic coherences are rapidly obscured by inhomogeneous dephasing. The longest-lived coherences in these systems arise from delocalized vibrations on the ground electronic state that are enhanced by a nonadiabatic Raman excitation process. These characterize the initial excited-state dynamics. 2D oscillation maps are beginning to isolate the medium lifetime vibronic coherences that report on subsequent stages of the excited-state dynamics.

    更新日期:2018-07-14
  • Enhancing Analytical Separations Using Super-Resolution Microscopy
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Nicholas A. Moringo, Hao Shen, Logan D.C. Bishop, Wenxiao Wang, Christy F. Landes

    Super-resolution microscopy is becoming an invaluable tool to investigate structure and dynamics driving protein interactions at interfaces. In this review, we highlight the applications of super-resolution microscopy for quantifying the physics and chemistry that occur between target proteins and stationary-phase supports during chromatographic separations. Our discussion concentrates on the newfound ability of super-resolved single-protein spectroscopy to inform theoretical parameters via quantification of adsorption-desorption dynamics, protein unfolding, and nanoconfined transport.

    更新日期:2018-07-14
  • Computational Design of Clusters for Catalysis
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Elisa Jimenez-Izal, Anastassia N. Alexandrova

    When small clusters are studied in chemical physics or physical chemistry, one perhaps thinks of the fundamental aspects of cluster electronic structure, or precision spectroscopy in ultracold molecular beams. However, small clusters are also of interest in catalysis, where the cold ground state or an isolated cluster may not even be the right starting point. Instead, the big question is: What happens to cluster-based catalysts under real conditions of catalysis, such as high temperature and coverage with reagents? Myriads of metastable cluster states become accessible, the entire system is dynamic, and catalysis may be driven by rare sites present only under those conditions. Activity, selectivity, and stability are highly dependent on size, composition, shape, support, and environment. To probe and master cluster catalysis, sophisticated tools are being developed for precision synthesis, operando measurements, and multiscale modeling. This review intends to tell the messy story of clusters in catalysis.

    更新日期:2018-07-14
  • Exploring Energy Landscapes
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    David J. Wales

    Recent advances in the potential energy landscapes approach are highlighted, including both theoretical and computational contributions. Treating the high dimensionality of molecular and condensed matter systems of contemporary interest is important for understanding how emergent properties are encoded in the landscape and for calculating these properties while faithfully representing barriers between different morphologies. The pathways characterized in full dimensionality, which are used to construct kinetic transition networks, may prove useful in guiding such calculations. The energy landscape perspective has also produced new procedures for structure prediction and analysis of thermodynamic properties. Basin-hopping global optimization, with alternative acceptance criteria and generalizations to multiple metric spaces, has been used to treat systems ranging from biomolecules to nanoalloy clusters and condensed matter. This review also illustrates how all this methodology, developed in the context of chemical physics, can be transferred to landscapes defined by cost functions associated with machine learning.

    更新日期:2018-07-14
  • Dynamics at Conical Intersections
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Michael S. Schuurman, Albert Stolow

    The nonadiabatic coupling of electronic and vibrational degrees of freedom is the defining feature of electronically excited states of polyatomic molecules. Once considered a theoretical curiosity, conical intersections (CIs) are now generally accepted as being the dominant source of coupled charge and vibrational energy flow in molecular excited states. Passage through CIs leads to the conversion of electronic to vibrational energy, which drives the ensuing photochemistry, isomerization being a canonical example. It has often been remarked that the CI may be thought of as a transition state in the excited state. As such, we expect that both the direction and the velocity of approach to the CI will matter. We explore this suggestion by looking for dynamical aspects of passage through CIs and for analogies with well-known concepts from ground-state reaction dynamics. Great progress has been made in the development of both experimental techniques and ab initio dynamics simulations, to a degree that direct comparisons may now be made. Here we compare time-resolved photoelectron spectroscopy results with on-the-fly ab initio multiple spawning calculations of the experimental observables, thereby validating each. We adopt a phenomenological approach and specifically concentrate on the excited-state dynamics of the C=C bond in unsaturated hydrocarbons. In particular, we make use of selective chemical substitution (such as replacing an H atom by a methyl group) so as to alter the inertia of certain vibrations relative to others, thus systematically varying (mass-weighted) directions and velocities of approach to a CI. Chemical substituents, however, may affect both the nuclear and electronic components of the total wave function. The former, which we call an inertial effect, influences the direction and velocity of approach. The latter, which we call a potential effect, modifies the electronic structure and therefore the energetic location and topography of the potential energy surfaces involved. Using a series of examples, we discuss both types of effects. We argue that there is a need for dynamical pictures and simple models of nonadiabatic dynamics at CIs and hope that the phenomenology presented here will help inspire such developments.

    更新日期:2018-07-14
  • Elementary Chemical Reactions in Surface Photocatalysis
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Qing Guo, Chuanyao Zhou, Zhibo Ma, Zefeng Ren, Hongjun Fan, Xueming Yang

    Photocatalytic hydrogen evolution and organic degradation on oxide materials have been extensively investigated in the last two decades. Great efforts have been dedicated to the study of photocatalytic reaction mechanisms of a variety of molecules on TiO2 surfaces by using surface science methods under ultra-high vacuum (UHV) conditions, providing fundamental understanding of surface chemical reactions in photocatalysis. In this review, we summarize the recent progress in the study of photocatalysis of several important species (water, methanol, and aldehydes) on different TiO2 surfaces. The results of these studies have provided us deep insights into the elementary processes of surface photocatalysis and stimulated a new frontier of research in this area. Based on the results of these studies, a new dynamics-based photocatalysis model is also discussed.

    更新日期:2018-07-14
  • Computational Photophysics in the Presence of an Environment
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Juan J. Nogueira, Leticia González

    Most processes triggered by ultraviolet (UV) or visible (vis) light in nature take place in complex biological environments. The first step in these photophysical events is the excitation of the absorbing system or chromophore to an electronically excited state. Such an excitation can be monitored by the UV-vis absorption spectrum. A precise calculation of the UV-vis spectrum of a chromophore embedded in an environment is a challenging task that requires the consideration of several ingredients, besides an accurate electronic-structure method for the excited states. Two of the most important are an appropriate description of the interactions between the chromophore and the environment and accounting for the vibrational motion of the whole system. In this contribution, we review the most common theoretical methodologies to describe the environment (including quantum mechanics/continuum and quantum mechanics/molecular mechanics models) and to account for vibrational sampling (including Wigner sampling and molecular dynamics). Further, we illustrate in a series of examples how the lack of these ingredients can lead to a wrong interpretation of the electronic features behind the UV-vis absorption spectrum.

    更新日期:2018-07-14
  • Sensing Chirality with Rotational Spectroscopy
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Sérgio R. Domingos, Cristóbal Pérez, Melanie Schnell

    Chiroptical spectroscopy techniques for the differentiation of enantiomers in the condensed phase are based on an established paradigm that relies on symmetry breaking using circularly polarized light. We review a novel approach for the study of chiral molecules in the gas phase using broadband rotational spectroscopy, namely microwave three-wave mixing, which is a coherent, nonlinear, and resonant process. This technique can be used to generate a coherent molecular rotational signal that can be detected in a manner similar to that in conventional Fourier transform microwave spectroscopy. The structure (and thermal distribution of conformations), handedness, and enantiomeric excess of gas-phase samples can be determined unambiguously by employing tailored microwave fields. We discuss the theoretical and experimental aspects of the method, the significance of the first demonstrations of the technique for enantiomer differentiation, and the method's rapid advance into a robust choice to study molecular chirality in the gas phase. Very recently, the microwave three-wave mixing approach was extended to enantiomer-selective population transfer, an important step toward spatial enantiomer separation on the fly.

    更新日期:2018-07-14
  • Membrane-Mediated Cooperativity of Proteins
    Annu. Rev. Phys. Chem. (IF 13.738) Pub Date : 2018-04-20
    Thomas R. Weikl

    Besides direct protein–protein interactions, indirect interactions mediated by membranes play an important role for the assembly and cooperative function of proteins in membrane shaping and adhesion. The intricate shapes of biological membranes are generated by proteins that locally induce membrane curvature. Indirect curvature-mediated interactions between these proteins arise because the proteins jointly affect the bending energy of the membranes. These curvature-mediated interactions are attractive for crescent-shaped proteins and are a driving force in the assembly of the proteins during membrane tubulation. Membrane adhesion results from the binding of receptor and ligand proteins that are anchored in the apposing membranes. The binding of these proteins strongly depends on nanoscale shape fluctuations of the membranes, leading to a fluctuation-mediated binding cooperativity. A length mismatch between receptor–ligand complexes in membrane adhesion zones causes repulsive curvature-mediated interactions that are a driving force for the length-based segregation of proteins during membrane adhesion.

    更新日期:2018-07-14
  • Molecules at Solid Surfaces: A Personal Reminiscence
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • From 50 Years Ago, the Birth of Modern Liquid-State Science
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Quantum State–Resolved Studies of Chemisorption Reactions
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Molecular Photofragmentation Dynamics in the Gas and Condensed Phases
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Coherent Light Sources at the Nanoscale
    Annu. Rev. Phys. Chem. (IF 13.738) 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 with cavity sizes much larger 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:2018-02-22
  • Progress Toward a Molecular Mechanism of Water Oxidation in Photosystem II
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Computer Simulations of Intrinsically Disordered Proteins
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • 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 13.738) 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:2018-02-22
  • Development of New Density Functional Approximations
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Criegee Intermediates: What Direct Production and Detection Can Teach Us About Reactions of Carbonyl Oxides
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Phospholipid Bilayers: Stability and Encapsulation of Nanoparticles
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Ice Surfaces
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Metal-Free Motifs for Solar Fuel Applications
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Ion–Molecule Reaction Dynamics
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Computational Analysis of Vibrational Sum Frequency Generation Spectroscopy
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Hot Charge Carrier Transmission from Plasmonic Nanostructures
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Calculating Natural Optical Activity of Molecules from First Principles
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Random-Phase Approximation Methods
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • The Hydrated Electron
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Ultrafast X-Ray Crystallography and Liquidography
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Roaming: A Phase Space Perspective
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • Extending Quantum Chemistry of Bound States to Electronic Resonances
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
  • The Importance of Being Inconsistent
    Annu. Rev. Phys. Chem. (IF 13.738) 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:2018-02-22
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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