Annual review of physical chemistry最新文献

Upconverting nanoparticles (UCNPs) compose a class of luminescent materials that utilize the unique wavelength-converting properties of lanthanide (Ln) ions for light-harvesting applications, photonics technologies, and biological imaging and sensing experiments. Recent advances in UCNP design have shed light on the properties of local color centers, both intrinsic and controllably induced, within these materials and their potential influence on UCNP photophysics. In this review, we describe fundamental studies of color centers in Ln-based materials, including research into their origins and their roles in observed photodarkening and photobrightening mechanisms. We place particular focus on the new functionalities that are enabled by harnessing the properties of color centers within Ln-doped nanocrystals, illustrated through applications in afterglow-based bioimaging, X-ray detection, all-inorganic nanocrystal photoswitching, and fully rewritable optical patterning and memory.

Atmospheric aerosols exert a significant but highly uncertain effect on the global climate, and roughly half of these particles originate as small clusters formed by collisions between atmospheric trace vapors. These particles typically consist of acids, bases, and water, stabilized by salt bridge formation and a network of strong hydrogen bonds. We review spectroscopic studies of this process, focusing on the clusters likely to be involved in the first steps of particle formation and the intermolecular interactions governing their stability. These studies typically focus on determining structure and stability and have shown that acid-base chemistry in the cluster may violate chemical intuition derived from solution-phase behavior and that hydration of these clusters is likely to be complex to describe. We also suggest fruitful areas for extension of these studies and alternative spectroscopic techniques that have not yet been applied to this problem.

The photoacid dynamics of fluorescent proteins include both electronic excited- and ground-state mechanisms of proton transfer. The associated characteristic timescales of these reactions range over many orders of magnitude, and the tunneling, barrier crossing, and relevant thermodynamics have in certain cases been linked to coherent nuclear motion. We review the literature and summarize the experiments and theory that demonstrate proton tunneling in the electronic ground state of the green fluorescent protein (GFP). We also discuss the excited-state proton-transfer reaction of GFP that takes place on the picosecond timescale. Although this reaction has been investigated using several vibrational spectroscopic methods, the interpretation remains unsettled. We discuss recent advances as well as remaining questions, in particular those related to the vibrational mode couplings that involve low-frequency modulations of chromophore vibrations on the timescale of proton transfer.

Light-driven phenomena in organic molecular aggregates underpin several mechanisms relevant to optoelectronic applications. Modeling these processes is essential for aiding the design of new materials and optimizing optoelectronic devices. In this review, we cover the use of different atomistic models, excited-state dynamics, and transport approaches for understanding light-activated phenomena in molecular aggregates, including radiative and nonradiative decay pathways. We consider both intra- and intermolecular mechanisms and focus on the role of conical intersections as facilitators of internal conversion. We explore the use of the exciton models for Frenkel and charge transfer states and the electronic structure methods and algorithms commonly applied for excited-state dynamics. Throughout the review, we analyze the approximations employed for the simulation of internal conversion, intersystem crossing, and reverse intersystem crossing rates and analyze the molecular processes behind single fission, triplet-triplet annihilation, Dexter energy transfer, and Förster energy transfer.

High-resolution vibrational spectra of C-H, O-H, and N-H stretches depend on both molecular conformation and environment as well as provide a window into the frequencies of many other vibrational degrees of freedom as a result of mode mixing. We review current theoretical strategies that are being deployed to both aid and guide the analysis of the data that are encoded in these spectra. The goal is to enhance the power of vibrational spectroscopy as a tool for probing conformational preferences, hydrogen bonding effects away from equilibrium, and energy flow pathways. Recent years have seen an explosion of new methods and strategies for solving the nuclear Schrödinger equation. Rather than attempt a comprehensive review, this work highlights specific molecular systems that we have chosen as representing bonding motifs that are important to chemistry and biology. We focus on the choices theoretical chemists make regarding the level of electronic structure theory, the representation of the potential energy surface, the selection of coordinates, preferences in basis sets, and methods of solution.

Phillip L. Geissler made important contributions to the statistical mechanics of biological polymers, heterogeneous materials, and chemical dynamics in aqueous environments. He devised analytical and computational methods that revealed the underlying organization of complex systems at the frontiers of biology, chemistry, and materials science. In this retrospective we celebrate his work at these frontiers.

A significant advantage of organic semiconductors over many of their inorganic counterparts is solution processability. However, solution processing commonly yields heterogeneous films with properties that are highly sensitive to the conditions and parameters of casting and processing. Measuring the key properties of these materials in situ, during film production, can provide new insight into the mechanism of these processing steps and how they lead to the emergence of the final organic film properties. The excited-state dynamics is often of import in photovoltaic, electronic, and light-emitting devices. This review focuses on single-shot transient absorption, which measures a transient spectrum in a single shot, enabling the rapid measurement of unstable chemical systems such as organic films during their casting and processing. We review the principles of instrument design and provide examples of the utility of this spectroscopy for measuring organic films during their production.

The magneto-optical signatures of colloidal noble metal nanostructures, spanning both discrete nanoclusters (<2 nm) and plasmonic nanoparticles (>2 nm), exhibit rich structure-property correlations, impacting applications including photonic integrated circuits, light modulation, applied spectroscopy, and more. For nanoclusters, electron doping and single-atom substitution modify both the intensity of the magneto-optical response and the degree of transient spin polarization. Nanoparticle size and morphology also modulate the magnitude and polarity of plasmon-mediated magneto-optical signals. This intimate interplay between nanostructure and magneto-optical properties becomes especially apparent in magnetic circular dichroism (MCD) and magnetic circular photoluminescence (MCPL) spectroscopic data. Whereas MCD spectroscopy informs on a metal nanostructure's steady-state extinction properties, its MCPL counterpart is sensitive to electronic spin and orbital angular momenta of transiently excited states. This review describes the size- and structure-dependent magneto-optical properties of nanoscale metals, emphasizing the increasingly important role of MCPL in understanding transient spin properties and dynamics.

Predicting the whole process of a chemical reaction while solving kinetic equations presents an opportunity to realize an on-the-fly kinetic simulation that directly discovers chemical reactions with their product yields. Such a simulation avoids the combinatorial explosion of reaction patterns to be examined by narrowing the search space based on the kinetic analysis of the reaction path network, and would open a new paradigm beyond the conventional two-step approach, which requires a reaction path network prior to performing a kinetic simulation. The authors addressed this issue and developed a practical method by combining the artificial force induced reaction method with the rate constant matrix contraction method. Two algorithms are available for this purpose: a forward mode with reactants as the input and a backward mode with products as the input. This article first numerically verifies these modes for known reactions and then demonstrates their application to the actual reaction discovery. Finally, the challenges of this method and the prospects for ab initio reaction discovery are discussed.

Localized surface plasmon resonances (LSPRs) in metallic nanostructures result in subwavelength optical confinement that enhances light-matter interactions, for example, aiding the sensitivity of surface spectroscopies. The dissipation of surface plasmons as electronic and vibrational excitations sets the limit for field confinement but also provides opportunities for photochemistry, photocatalysis, and photothermal heating. Optimization for either goal requires a deeper understanding of this photothermalization process. In this review, we focus on recent insights into the physics and dynamics governing photothermalization of LSPRs in metallic nanostructures, emphasizing comparisons between the steady-state behavior and ultrafast time-resolved studies. The differences between these regimes inform how to best optimize plasmonic systems for applications under relatively low-intensity, continuous illumination (e.g., sunlight).