Annual review of physical chemistry最新文献

Inspired by the success of graphene, two-dimensional (2D) materials have been at the forefront of advanced (opto-)nanoelectronics and energy-related fields owing to their exotic properties like sizable bandgaps, Dirac fermions, quantum spin Hall states, topological edge states, and ballistic charge carrier transport, which hold promise for various electronic device applications. Emerging main group elemental 2D materials, beyond graphene, are of particular interest due to their unique structural characteristics, ease of synthetic exploration, and superior property tunability. In this review, we present recent advances in atomic-scale studies of elemental 2D materials with an emphasis on synthetic strategies and structural properties. We also discuss the challenges and perspectives regarding the integration of elemental 2D materials into various heterostructures.

Ultrafast excitation of nanoparticles can excite the acoustic vibrational modes of the structure that correlate with the expansion coordinates. These modes are frequently seen in transient absorption experiments on metal nanoparticle samples and occasionally for semiconductors. The aim of this review is to give an overview of the physical chemistry of nanostructure acoustic vibrations. The issues discussed include the excitation mechanism, how to calculate the mode frequencies using continuum mechanics, and the factors that control vibrational damping. Recent results that demonstrate that the high frequencies inherent to the acoustic modes of nanomaterials trigger a viscoelastic response in surrounding liquids are also discussed, as well as vibrational coupling between nanostructures and mode hybridization within the nanostructures. Mode hybridization provides a way of manipulating the lifetimes of the acoustic modes, which is potentially useful for applications such as mass sensing.

Plasmonic nanomaterials are promising photocatalysts due to their large optical cross sections and facile generation of nanoscale hotspot regions. They have been used to drive a range of photochemical reactions, including H₂ dissociation, CO₂ reduction, and ammonia synthesis, offering an exciting approach to light-driven chemistry. Deepening our understanding of how energy can be controllably transferred from the plasmonic nanomaterial to proximal reactants should lead to improvements in the efficiency and selectivity in plasmonic photocatalysis. Here we provide a comprehensive overview of plasmonic properties and explore different energy partitioning pathways. We focus on the importance of mapping molecular potential energy landscapes to understand reactivity and describe recent advancements in spectroscopic techniques, such as ultrafast surface-enhanced Raman spectroscopy, electron microscopy, and electrochemistry, that can aid in understanding how plasmonic nanomaterials can be used to shape potential energy surfaces and modify chemical outcomes. Additionally, we explore innovative hybrid plasmonic nanostructures such as antenna-reactor complexes, plasmonic single-atom catalysts, plasmonic picocavities, and chiral plasmonic substrates, all of which show great promise in advancing the field of plasmon-driven chemistry.

The present autobiography recounts the author's education in the liberal arts, physics, and chemistry, and his participation in various developing stages of ab initio quantum chemistry from its beginning around 1950 to the present. His personal history is briefly noted.

This is a recollection of my scientific trajectory. When I look back, I consider myself to be very fortunate for being able to do something I love and on topics of my own will. I am not a competitive person and tend to shy away from the limelight. Nonetheless, I survived in my profession and eventually made some modest contributions, which are beyond what I would have expected. We often forget about the human aspect of scientific endeavor. After all, science is done by individuals; humans have emotions and make mistakes. The frustrations of failures, the joys of finding problems and solutions to them, and the passion for fulfilling curiosity are all parts of this endeavor. Throughout the years, many people-mentors, students, postdocs, collaborators, and colleagues-have accompanied me in this exciting and fruitful journey, for which I am deeply grateful and feel very lucky to have them.

The inversion of singlet and triplet states is a rare phenomenon, where, in opposition to Hund's first rule, singlet electronic states are stabilized relative to their triplet counterparts. The recent discovery of organic molecules exhibiting this inversion presents exciting new technological opportunities, such as addressing stability issues in organic light-emitting diodes (OLEDs). In this review, we describe fundamental molecular properties that can yield singlet-triplet inversion, generally ascribed to a phenomenon known as dynamic spin polarization. We discuss the systems in which singlet-triplet inversion was theoretically proposed, experimentally verified, and first implemented in an OLED device. We highlight key insights from the extensive computational work being carried out to understand the intricacies of these systems. Finally, we consider the outlook for future inverted singlet-triplet (IST) emitters.

Information is an important resource. Storing and retrieving information faithfully are huge challenges and many methods have been developed to understand the principles behind robust information processing. In this review, we focus on information storage and retrieval from the perspective of energetics, dynamics, and statistical mechanics. We first review the Hopfield model of associative memory, the classic energy-based model of memory. We then discuss generalizations and physical realizations of the Hopfield model. Finally, we highlight connections to energy-based neural networks used in deep learning. We hope this review inspires new directions along the lines of information storage and retrieval in physical systems.

The movement of charges through a chiral medium results in a spin-polarized charge current. This phenomenon, known as the chirality-induced spin selectivity (CISS) effect, enables control over spin populations without the need for magnetic components and operates at room temperature. CISS has been discovered in a range of chiral media and most prominently studied in chiral organic molecular species. Chiral hybrid organic-inorganic perovskite semiconductors combine the unique and functional aspects of inorganic semiconductors with chiral molecules. The inorganic component borrows the homochirality of the organic component to yield a unique family of highly tunable chiral semiconductors, where the enantiomeric purity is defined by the organic component. Semiconductors already form the backbone of modern-day technologies. Adding chirality and control over spin through CISS provides new avenues for creative technological development. This review is intended to be an introduction to these unique systems and the demonstrations of CISS and spin control.

Molecular machines transduce free energy between different forms throughout all living organisms. Unlike their macroscopic counterparts, molecular machines are characterized by stochastic fluctuations, overdamped dynamics, and soft components, and operate far from thermodynamic equilibrium. In addition, information is a relevant free energy resource for molecular machines, leading to new modes of operation for nanoscale engines. Toward the objective of engineering synthetic nanomachines, an important goal is to understand how molecular machines transduce free energy to perform their functions in biological systems. In this review, we discuss the nonequilibrium thermodynamics of free energy transduction within molecular machines, with a focus on quantifying energy and information flows between their components. We review results from theory, modeling, and inference from experiments that shed light on the internal thermodynamics of molecular machines, and ultimately explore what we can learn from considering these interactions.

With markedly different reaction conditions compared to the chemistry of the outside atmosphere, indoor air chemistry poses new challenges to the scientific community that require combined experimental and computational efforts. Here, we review molecular dynamics simulations that have contributed to the mechanistic understanding of the complex dynamics of organic compounds at indoor surfaces and their interplay with experiments and indoor air models. We highlight the rich interactions between volatile organic compounds and silica and titanium dioxide surfaces, serving as proxies for glasses and paints, as well as the dynamics of skin oil lipids and their oxidation products, which sensitively affect the quality of indoor air in crowded environments. As the studies we review here are pioneering in the rapidly emerging field of indoor chemistry, we provide suggestions for increasing the potentially important role that molecular simulations can continue to play.