Annual review of physical chemistry最新文献

Density functional theory (DFT) is widely used to describe electronic structure in chemistry, physics, and materials science. Its accuracy is constrained by the exchange-correlation (XC) functional, which remains an approximation in all practical implementations. In contrast, wavefunction theory (WFT) offers a systematically improvable description of electron correlation, albeit at a higher computational cost. The complementary strengths of DFT and WFT have motivated efforts to connect the two. Historically, such connections have centered on total energies and electron densities, but recent advances have expanded these bridges to include XC potentials and energy densities. This review highlights strategies for translating quantities from WFT to DFT, with a focus on extracting XC potentials and energy densities from wavefunctions. Challenges in using finite basis sets, and potential solutions to this problem, are highlighted. These approaches offer insights into the structure of the exact XC functional and practical tools for developing next-generation approximations with improved accuracy and generalizability.

Many technological and environmental processes take place at mineral-water interfaces, which makes detailed knowledge of the structure and interactions at aqueous mineral interfaces essential to understand these processes. Since mineral surfaces could become charged upon contact with electrolyte solutions, the interfacial water structure and properties are also influenced by the interactions of water and ions in solution with this surface charge. A particularly promising strategy for the investigation of neutral and charged mineral-water interfaces is the combination of nonlinear optical spectroscopy with atomic force microscopy (AFM). Nonlinear optical spectroscopy provides insights into the water orientation and dynamics at the interface, while AFM can resolve the interfacial water density and forces. In this review, we discuss how nonlinear optical spectroscopy and AFM can be used to investigate mineral-water interfaces and advance our fundamental understanding of aqueous mineral interfaces.

Recent advances in experimental and theoretical physical chemistry have provided a path for a new technique for routine chiral analysis of small organic molecules. Chiral tag rotational spectroscopy uses chiral derivatization to convert the enantiomers of an analyte into spectroscopically distinct diastereomers. The derivatization is achieved by forming molecular complexes between the analyte and a small, chiral molecule-the tag-via noncovalent interactions. These chiral tag complexes are formed in the molecular beam expansion used to inject samples into Fourier transform microwave spectrometers. Rotational spectroscopy analysis, guided by computational chemistry methods that model the geometries of the low-energy isomers of the tag complexes, is used to assign the absolute configuration of the analyte. Intensity changes in the rotational spectrum between measurements using racemic and enantiopure tag samples are used to determine the enantiomeric excess. A key feature of chiral tag rotational spectroscopy is that chiral analysis can be performed without any reference samples of the analyte.

Membraneless organelles, also known as biomolecular condensates, formed via liquid-liquid phase separation (LLPS), have been proposed to play essential roles in diverse cellular processes. Their dysregulation has been implicated in various neurodegenerative diseases, highlighting the need to understand the principles governing their formation. A key challenge is to decode the sequence-encoded rules that tune the thermodynamics and dynamics of biomolecular condensation. Alongside experimental advances, computational modeling at mesoscopic, coarse-grained, and atomistic resolutions has emerged as a powerful approach to probe LLPS. In this review, we summarize recent progress in the predictive modeling of biomolecular phase separation, with a focus on residue-level coarse-grained models that serve as a bridge between mesoscopic models used in field-theoretic simulations and atomistic models. We highlight the approaches adopted in developing models to study LLPS and provide a perspective on directions for future improvement. We conclude by proposing a parameterization strategy that combines multiscale simulations with experimental approaches to uncover the molecular mechanisms underlying condensate formation, maturation, and dysfunction.

This review describes insights obtained from recent studies of unimolecular and bimolecular reactions of small carbenes in the gas phase and cryogenic environments. Following a description of what determines the singlet-triplet splitting in carbenes, we discuss the challenges involved in producing carbenes in concentrations sufficient for studying their reactions. We document the methods developed for their preparation and the array of spectroscopic techniques available for their characterization. The review emphasizes recent progress in studies of hydroxycarbenes and small alkyl carbenes that easily isomerize to more stable isomers. The studies of unimolecular reactions of hydroxycarbenes show how quantum mechanical tunneling determines their lifetimes. A new carbonyl-ene mechanism has been demonstrated in the biomolecular reactions of hydroxymethylene and methylhydroxycarbenes. We evaluate the impact of these new results on chemical processes relevant to atmospheric, planetary, and interstellar environments and highlight the importance of collaboration between theory and experiment in interpreting mechanisms.

Coupling molecules to the quantized radiation field inside an optical cavity creates a set of new photon-matter hybrid states, so-called polaritons. Recent experiments have demonstrated that molecular polaritons can lead to modifications of excited-state dynamics and spectroscopy, photochemistry, and ground-state chemical reactivities. We review the fundamental theory of molecular polaritons under collective light-matter coupling, where many molecules are simultaneously coupled to the cavity mode. Our discussion is based on model systems that effectively capture the essential physics of experiments, allowing one to obtain analytic theories and valuable insights into the microscopic mechanisms in polariton dynamics and spectroscopy, photochemistry, and vibrational strong coupling-modified chemistry.

This review concerns light-to-chemical energy conversion, focusing on approaches that could be driven by terrestrial sunlight to produce hydrogen and/or reduce carbon dioxide. Recent advances in photocatalytic (PC) and photoelectrocatalytic (PEC) materials are covered. In both approaches, the electron-hole pairs that are created by photon absorption must travel in specific directions to the sites that mediate multielectron bond making/breaking redox reactions. Thermodynamic requirements for materials stability are described, although some recently discovered materials appear to be exceptions. For PC materials, the importance of rate matching between reduction and oxidation processes and the mass transfer of intermediates and products is emphasized. Surprisingly, metal sulfides appear to be promising for PC carbon dioxide reduction. For PEC materials, recent work elucidating the elementary step mechanism for oxygen evolution on metal oxides and the discovery of chalcogen-based photocathode materials capable of sustained light-driven CO₂ reduction are discussed.

Recent advancements in transmission electron microscopy (TEM) have substantially expanded our capability to observe nanocrystals at unprecedented spatial and temporal resolutions. Innovations in TEM instruments, specimen preparation, and imaging modality have overcome historical limitations related to radiation damage, weak contrast for light elements, 2D projection limitations, and high-vacuum constraints. Additionally, advanced image processing techniques, particularly those incorporating machine learning, have enhanced data interpretation by enabling denoising, segmentation, and quantitative analysis. These advancements now enable the atomic-scale visualization of structural motifs, defects, strain distributions, and dynamic structural transformations of nanocrystals in realistic environments, including liquids and gases. The integration of these emerging TEM techniques promises novel insights into nanoscale processes that directly link atomic structure and dynamics to functional properties, thus significantly advancing the ultimate goal of materials by design.

Complex spatiotemporal correlations direct heterogeneous reactions spanning from the atomic- to meso-length scales with illustrations ranging from single-molecule adsorption to the oxidation of graphitic materials. Capturing the on-surface dynamics that underpin such processes benefits from spatially resolved and real-time in situ characterization of surface morphologies and adsorbed species, especially when paired with molecular scattering systems that provide tight control of incident molecular energy and approach geometry. Direct visualization shows that site-specific reactivity, correlated surface fluctuations, and structurally dependent reaction rates are interrelated to the on-surface fate of scattered species. Recent advances in neutral helium atom scattering are also presented as pathways for elucidating surface electron-phonon coupling dynamics. Overall, experiments presented herein represent a new direction for the interrogation of on-surface dynamics in which incident kinematics and energetics are tunable control parameters that influence time-evolving surface dynamics-and provide an incisive complement to traditional scattering experiments that monitor volatile products and scattered species.

Ultrafast core-to-valence transient absorption spectroscopy has emerged as a powerful technique for monitoring nonequilibrium chemical dynamics with element and site specificity. Owing to advancements in the robust, tabletop generation of ultrafast extreme ultraviolet (XUV) and soft X-ray (SXR) pulses, this technique has been applied to great effect in investigating electronic excited-state dynamics in various gas-phase molecules. This review begins with an overview of the experimental advances that have enabled laboratory-scale XUV and SXR production with particular emphasis on high-harmonic generation, central to modern implementations of tabletop core-to-valence transient absorption spectroscopy. We then highlight a collection of landmark studies that demonstrate the unprecedented insights this technique yields into the site-specific excited-state dynamics governing photoinduced processes such as bond dissociation, conformational change, and electronic relaxation in gas-phase molecules. We conclude with an outlook on future frontiers, including control of excited-state dynamics, other nonlinear X-ray spectroscopies, and next-generation light sources.