Annual review of physical chemistry最新文献

Attosecond science requires a substantial rethinking of how to make measurements on very short timescales; how to acquire the necessary equipment, technology, and personnel; and how to build a set of laboratories for such experiments. This entails a rejuvenation of the author in many respects, in the laboratory itself, with regard to students and postdocs, and in generating funding for research. It also brings up questions of what it means to do attosecond science, and the discovery of the power of X-ray spectroscopy itself, which complements the short timescales addressed. The lessons learned, expressed in the meanderings of this autobiographical article, may be of benefit to others who try to reinvent themselves.

Crystallographic analysis relies on the scattering of quanta from arrays of atoms that populate a repeating lattice. While large crystals built of lattices that appear ideal are sought after by crystallographers, imperfections are the norm for molecular crystals. Additionally, advanced X-ray and electron diffraction techniques, used for crystallography, have opened the possibility of interrogating micro- and nanoscale crystals, with edges only millions or even thousands of molecules long. These crystals exist in a size regime that approximates the lower bounds for traditional models of crystal nonuniformity and imperfection. Accordingly, data generated by diffraction from both X-rays and electrons show increased complexity and are more challenging to conventionally model. New approaches in serial crystallography and spatially resolved electron diffraction mapping are changing this paradigm by better accounting for variability within and between crystals. The intersection of these methods presents an opportunity for a more comprehensive understanding of the structure and properties of nanocrystalline materials.

Recent theoretical and algorithmic developments have improved the accuracy with which path integral dynamics methods can include nuclear quantum effects in simulations of condensed-phase vibrational spectra. Such methods are now understood to be approximations to the delocalized classical Matsubara dynamics of smooth Feynman paths, which dominate the dynamics of systems such as liquid water at room temperature. Focusing mainly on simulations of liquid water and hexagonal ice, we explain how the recently developed quasicentroid molecular dynamics (QCMD), fast-QCMD, and temperature-elevated path integral coarse-graining simulations (Te PIGS) methods generate classical dynamics on potentials of mean force obtained by averaging over quantum thermal fluctuations. These new methods give very close agreement with one another, and the Te PIGS method has recently yielded excellent agreement with experimentally measured vibrational spectra for liquid water, ice, and the liquid-air interface. We also discuss the limitations of such methods.

Low-resolution coarse-grained (CG) models provide remarkable computational and conceptual advantages for simulating soft materials. In principle, bottom-up CG models can reproduce all structural and thermodynamic properties of atomically detailed models that can be observed at the resolution of the CG model. This review discusses recent progress in developing theory and computational methods for achieving this promise. We first briefly review variational approaches for parameterizing interaction potentials and their relationship to machine learning methods. We then discuss recent approaches for simultaneously improving both the transferability and thermodynamic properties of bottom-up models by rigorously addressing the density and temperature dependence of these potentials. We also briefly discuss exciting progress in modeling high-resolution observables with low-resolution CG models. More generally, we highlight the essential role of the bottom-up framework not only for fundamentally understanding the limitations of prior CG models but also for developing robust computational methods that resolve these limitations in practice.

Water-metal oxide interfaces are central to many phenomena and applications, ranging from material corrosion and dissolution to photoelectrochemistry and bioengineering. In particular, the discovery of photocatalytic water splitting on TiO₂ has motivated intensive studies of water-TiO₂ interfaces for decades. So far, a broad understanding of the interaction of water vapor with several TiO₂ surfaces has been obtained. However, much less is known about liquid water-TiO₂ interfaces, which are more relevant to many practical applications. Probing these complex systems at the molecular level is experimentally challenging and is sometimes possible only through computational studies. This review summarizes recent advances in the atomistic understanding, mostly through computational simulations, of the structure and dynamics of interfacial water on TiO₂ surfaces. The main focus is on the nature, molecular or dissociated, of water in direct contact with low-index defect-free crystalline surfaces. The hydroxyls resulting from water dissociation are essential in the photooxidation of water and critically affect the surface chemistry of TiO_2.

The phase state of aerosol particles can impact numerous atmospheric processes, including new particle growth, heterogeneous chemistry, cloud condensation nucleus formation, and ice nucleation. In this article, the phase transitions of inorganic, organic, and organic/inorganic aerosol particles are discussed, with particular focus on liquid-liquid phase separation (LLPS). The physical chemistry that determines whether LLPS occurs, at what relative humidity it occurs, and the resultant particle morphology is explained using both theoretical and experimental methods. The known impacts of LLPS on aerosol processes in the atmosphere are discussed. Finally, potential evidence for LLPS from field and chamber studies is presented. By understanding the physical chemistry of the phase transitions of aerosol particles, we will acquire a better understanding of aerosol processes, which in turn impact human health and climate.

Dynamical reweighting techniques aim to recover the correct molecular dynamics from a simulation at a modified potential energy surface. They are important for unbiasing enhanced sampling simulations of molecular rare events. Here, we review the theoretical frameworks of dynamical reweighting for modified potentials. Based on an overview of kinetic models with increasing level of detail, we discuss techniques to reweight two-state dynamics, multistate dynamics, and path integrals. We explore the natural link to transition path sampling and how the effect of nonequilibrium forces can be reweighted. We end by providing an outlook on how dynamical reweighting integrates with techniques for optimizing collective variables and with modern potential energy surfaces.

Reaction intermediates buried within a solid-liquid interface are difficult targets for physiochemical measurements. They are inherently molecular and locally dynamic, while their surroundings are extended by a periodic lattice on one side and the solvent dielectric on the other. Challenges compound on a metal-oxide surface of varied sites and especially so at its aqueous interface of many prominent reactions. Recently, phenomenological theory coupled with optical spectroscopy has become a more prominent tool for isolating the intermediates and their molecular dynamics. The following article reviews three examples of the SrTiO₃-aqueous interface subject to the oxygen evolution from water: reaction-dependent component analyses of time-resolved intermediates, a Fano resonance of a mode at the metal-oxide-water interface, and reaction isotherms of metastable intermediates. The phenomenology uses parameters to encase what is unknown at a microscopic level to then circumscribe the clear and macroscopically tuned trends seen in the spectroscopic data.

Experimental studies of the collision phenomena of submicrometer particles is a developing field. This review examines the range of phenomena that can be observed with new experimental approaches. The primary focus is on single-particle impact studies enabled by charge detection mass spectrometry (CDMS) implemented using the Aerosol Impact Spectrometer (AIS) at the University of California, San Diego. The AIS combines electrospray ionization, aerodynamic lens techniques, CDMS, and an electrostatic linear accelerator to study the dynamics of particle impact over a wide range of incident velocities. The AIS has been used for single-particle impact experiments on positively charged particles of diverse composition, including polystyrene latex spheres, tin particles, and ice grains, over a wide range of impact velocities. Detection schemes based on induced charge measurements and time-of-flight mass spectrometry have enabled measurements of the impact inelasticity through the determination of the coefficient of restitution, measurements of the angular distributions of scattered submicrometer particles, and the chemical composition and dissociation of solute molecules in hypervelocity ice grain impacts.

Micrometer-sized compartments play significant roles in driving heterogeneous transformations within atmospheric and biochemical systems as well as providing vehicles for drug delivery and novel reaction environments for the synthesis of industrial chemicals. Many reports now indicate that reaction kinetics are accelerated under microconfinement, for example, in sprays, thin films, droplets, aerosols, and emulsions. These observations are dramatic, posing a challenge to our understanding of chemical reaction mechanisms with potentially significant practical consequences for predicting the complex chemistry in natural systems. Here we introduce the idea of kinetic confinement, which is intended to provide a conceptual backdrop for understanding when and why microdroplet reaction kinetics differ from their macroscale analogs.