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Annu Rev Phys Chem 2022 Apr 4;73:377-402. Epub 2022 Feb 4.

The MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, State Key Laboratory of Physical Chemistry of Solid Surfaces, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen Key Laboratory of Analytical Molecular Nanotechnology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, China; email:

Optical microscopy has become an invaluable tool for investigating complex samples. Over the years, many advances to optical microscopes have been made that have allowed us to uncover new insights into the samples studied. Dynamic changes in biological and chemical systems are of utmost importance to study. Read More

Annu Rev Phys Chem 2022 Apr 4;73:403-428. Epub 2022 Feb 4.

Department of Electrical and Systems Engineering, Department of Materials Science and Engineering, and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA; email:

Two-dimensional organic-inorganic hybrid perovskites (2DHPs) consist of alternating anionic metal-halide and cationic organic layers. They have widely tunable structural and optical properties. We review the role of the organic cation in defining the structural and optical properties of 2DHPs through the example of lead iodide 2DHPs. Read More

Annu Rev Phys Chem 2022 Apr 3;73:453-477. Epub 2022 Feb 3.

School of Civil, Environmental and Chemical Engineering, Changwon National University, Changwon, South Korea; email:

All solid materials are created via nucleation. In this evolutionary process, nuclei form in solution or at interfaces, expand by monomeric growth and oriented attachment, and undergo phase transformation. Nucleation determines the location and size of nuclei, whereas growth controls the size, shape, and aggregation of newly formed nanoparticles. Read More

Annu Rev Phys Chem 2022 Apr 26;73:255-272. Epub 2022 Jan 26.

Department of Chemistry, University of California, Berkeley, California, USA; email:

We review a suite of stochastic vector computational approaches for studying the electronic structure of extended condensed matter systems. These techniques help reduce algorithmic complexity, facilitate efficient parallelization, simplify computational tasks, accelerate calculations, and diminish memory requirements. While their scope is vast, we limit our study to ground-state and finite temperature density functional theory (DFT) and second-order many-body perturbation theory. Read More

Annu Rev Phys Chem 2022 Apr 26;73:299-322. Epub 2022 Jan 26.

Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York, USA; email:

This review focuses on a recent class of path-integral-based methods for the simulation of nonadiabatic dynamics in the condensed phase using only classical molecular dynamics trajectories in an extended phase space. Specifically, a semiclassical mapping protocol is used to derive an exact, continuous, Cartesian variable path-integral representation for the canonical partition function of a system in which multiple electronic states are coupled to nuclear degrees of freedom. Building on this exact statistical foundation, multistate ring polymer molecular dynamics methods are developed for the approximate calculation of real-time thermal correlation functions. Read More

Annu Rev Phys Chem 2022 Apr 26;73:429-451. Epub 2022 Jan 26.

Chemistry Division, Naval Research Laboratory, Washington, DC, USA; email:

Molecular polaritons result from light-matter coupling between optical resonances and molecular electronic or vibrational transitions. When the coupling is strong enough, new hybridized states with mixed photon-material character are observed spectroscopically, with resonances shifted above and below the uncoupled frequency. These new modes have unique optical properties and can be exploited to promote or inhibit physical and chemical processes. Read More

Annu Rev Phys Chem 2022 Apr 26;73:323-347. Epub 2022 Jan 26.

Department of Chemistry, Aarhus University, Aarhus, Denmark; email:

We discuss how Coulomb explosion imaging (CEI), triggered by intense femtosecond laser pulses and combined with laser-induced alignment and covariance analysis of the angular distributions of the recoiling fragment ions, provides new opportunities for imaging the structures of molecules and molecular complexes. First, focusing on gas phase molecules, we show how the periodic torsional motion of halogenated biphenyl molecules can be measured in real time by timed CEI, and how CEI of one-dimensionally aligned difluoroiodobenzene molecules can uniquely identify four structural isomers. Next, focusing on molecular complexes formed inside He nano-droplets, we show that the conformations of noncovalently bound dimers or trimers, aligned in one or three dimensions, can be determined by CEI. Read More

Annu Rev Phys Chem 2022 Apr 26;73:349-375. Epub 2022 Jan 26.

Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois, USA; email:

Excitation energy transfer (EET) is fundamental to many processes in chemical and biological systems and carries significant implications for the design of materials suitable for efficient solar energy harvest and transport. This review discusses the role of intramolecular vibrations on the dynamics of EET in nonbonded molecular aggregates of bacteriochlorophyll, a perylene bisimide, and a model system, based on insights obtained from fully quantum mechanical real-time path integral results for a Frenkel exciton Hamiltonian that includes all vibrational modes of each molecular unit at finite temperature. Generic trends, as well as features specific to the vibrational characteristics of the molecules, are identified. Read More

Annu Rev Phys Chem 2022 Apr 21;73:273-297. Epub 2022 Jan 21.

Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York, USA; email:

Multidimensional optical spectra are measured from the response of a material system to a sequence of laser pulses and have the capacity to elucidate specific molecular interactions and dynamics whose influences are absent or obscured in a conventional linear absorption spectrum. Interpretation of complex spectra is supported by theoretical modeling of the spectroscopic observable, requiring implementation of quantum dynamics for coupled electrons and nuclei. Performing numerically correct quantum dynamics in this context may pose computational challenges, particularly in the condensed phase. Read More

Annu Rev Phys Chem 2022 Apr 19;73:233-253. Epub 2022 Jan 19.

Department of Chemistry, Brown University, Providence, Rhode Island, USA; email:

Photoelectron spectroscopy combined with quantum chemistry has been a powerful approach to elucidate the structures and bonding of size-selected boron clusters (B), revealing a prevalent planar world that laid the foundation for borophenes. Investigations of metal-doped boron clusters not only lead to novel structures but also provide important information about the metal-boron bonds that are critical to understanding the properties of boride materials. The current review focuses on recent advances in transition-metal-doped boron clusters, including the discoveries of metal-boron multiple bonds and metal-doped novel aromatic boron clusters. Read More

Annu Rev Phys Chem 2022 Apr 19;73:209-231. Epub 2022 Jan 19.

Department of Chemistry, University of Copenhagen, Copenhagen, Denmark; email:

The vibrational spectroscopy of the water dimer provides an understanding of basic hydrogen bonding in water clusters, and with about one water dimer for every 1,000 water molecules, it plays a critical role in atmospheric science. Here, we review how the experimental and theoretical progress of the past decades has improved our understanding of water dimer vibrational spectroscopy under both cold and warm conditions. We focus on the intramolecular OH-stretching transitions of the donor unit, because these are the ones mostly affected by dimer formation and because their assignment has proven a challenge. Read More

Annu Rev Phys Chem 2022 Apr 5;73:187-208. Epub 2022 Jan 5.

PULSE Institute, SLAC National Accelerator Laboratory and Stanford University, Menlo Park, California, USA; email:

The atomic specificity of X-ray spectroscopies provides a distinct perspective on molecular electronic structure. For 3 metal coordination and organometallic complexes, the combination of metal- and ligand-specific X-ray spectroscopies directly interrogates metal-ligand covalency-the hybridization of metal and ligand electronic states. Resonant inelastic X-ray scattering (RIXS), the X-ray analog of resonance Raman scattering, provides access to all classes of valence excited states in transition-metal complexes, making it a particularly powerful means of characterizing the valence electronic structure of 3 metal complexes. Read More

Annu Rev Phys Chem 2022 Apr 4;73:163-186. Epub 2022 Jan 4.

Institut für Physikalische Chemie, Theoretische Chemie, Universität Göttingen, Göttingen, Germany; email:

In the past two decades, machine learning potentials (MLPs) have reached a level of maturity that now enables applications to large-scale atomistic simulations of a wide range of systems in chemistry, physics, and materials science. Different machine learning algorithms have been used with great success in the construction of these MLPs. In this review, we discuss an important group of MLPs relying on artificial neural networks to establish a mapping from the atomic structure to the potential energy. Read More

Annu Rev Phys Chem 2022 Apr 22;73:141-162. Epub 2021 Dec 22.

Department of Chemistry, University of Iowa, Iowa City, Iowa, USA; email:

Surface-enhanced Raman scattering (SERS), a powerful technique for trace molecular detection, depends on chemical and electromagnetic enhancements. While recent advances in instrumentation and substrate design have expanded the utility, reproducibility, and quantitative capabilities of SERS, some challenges persist. In this review, advances in quantitative SERS detection are discussed as they relate to intermolecular interactions, surface selection rules, and target molecule solubility and accessibility. Read More

Annu Rev Phys Chem 2022 Apr 15;73:117-140. Epub 2021 Dec 15.

Department of Physics, Rutgers University at Newark, Newark, New Jersey, USA; email:

Time-dependent density functional theory has emerged as a method of choice for calculations of spectra and response properties in physics, chemistry, and biology, with its system-size scaling enabling computations on systems much larger than otherwise possible. While increasingly complex and interesting systems have been successfully tackled with relatively simple functional approximations, there has also been increasing awareness that these functionals tend to fail for certain classes of approximations. Here I review the fundamental challenges the approximate functionals have in describing double excitations and charge-transfer excitations, which are two of the most common impediments for the theory to be applied in a black-box way. Read More

Annu Rev Phys Chem 2022 Apr 10;73:73-96. Epub 2021 Dec 10.

Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, USA; email:

Advances in atomic, molecular, and optical physics techniques allowed the cooling of simple molecules down to the ultracold regime ([Formula: see text]1 mK) and opened opportunities to study chemical reactions with unprecedented levels of control. This review covers recent developments in studying bimolecular chemistry at ultralow temperatures. We begin with a brief overview of methods for producing, manipulating, and detecting ultracold molecules. Read More

Annu Rev Phys Chem 2022 Apr 9;73:97-116. Epub 2021 Dec 9.

School of Chemistry, University of Southampton, Southampton, United Kingdom; email:

As the volume of data associated with scientific research has exploded over recent years, the use of digital infrastructures to support this research and the data underpinning it has increased significantly. Physical chemists have been making use of eScience infrastructures since their conception, but in the last five years their usage has increased even more. While these infrastructures have not greatly affected the chemistry itself, they have in some cases had a significant impact on how the research is undertaken. Read More

Annu Rev Phys Chem 2022 Apr 6;73:43-71. Epub 2021 Dec 6.

Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA; email:

Chemical manifestations of strong light-matter coupling have recently been a subject of intense experimental and theoretical studies. Here we review the present status of this field. Section 1 is an introduction to molecular polaritonics and to collective response aspects of light-matter interactions. Read More

Annu Rev Phys Chem 2022 Apr 11;73:21-42. Epub 2021 Nov 11.

Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing, China; email:

Photoexcited molecules convert light into chemical and mechanical energy through changes in electronic and nuclear structure that take place on femtosecond timescales. Gas phase ultrafast electron diffraction (GUED) is an ideal tool to probe the nuclear geometry evolution of the molecules and complements spectroscopic methods that are mostly sensitive to the electronic state. GUED is a weak and passive probing tool that does not alter the molecular properties during the probing process and is sensitive to the spatial distribution of charge in the molecule, including both electrons and nuclei. Read More

Annu Rev Phys Chem 2022 Apr 1;73:1-19. Epub 2021 Nov 1.

Department of Chemistry and Biochemistry, Ohio State University, Columbus, Ohio 43210, USA; email:

Knowledge of protein structure is crucial to our understanding of biological function and is routinely used in drug discovery. High-resolution techniques to determine the three-dimensional atomic coordinates of proteins are available. However, such methods are frequently limited by experimental challenges such as sample quantity, target size, and efficiency. Read More

Annu Rev Phys Chem 2021 Apr;72:541-564

Department of Chemistry, Pritzker School of Molecular Engineering, James Franck Institute, and Chicago Center for Theoretical Chemistry, The University of Chicago, Chicago, Illinois 60637, USA; email:

Kohn-Sham density functional theory with the available exchange-correlation functionals is less accurate for strongly correlated systems, which require a multiconfigurational description as a zero-order function, than for weakly correlated systems, and available functionals of the spin densities do not accurately predict energies for many strongly correlated systems when one uses multiconfigurational wave functions with spin symmetry. Furthermore, adding a correlation functional to a multiconfigurational reference energy can lead to double counting of electron correlation. Multiconfiguration pair-density functional theory (MC-PDFT) overcomes both obstacles, the second by calculating the quantum mechanical part of the electronic energy entirely by a functional, and the first by using a functional of the total density and the on-top pair density rather than the spin densities. Read More

Annu Rev Phys Chem 2021 04;72:445-465

Institut de Chimie Physique, CNRS UMR 8000, Université Paris-Saclay, 91405 Orsay, France; email:

Ionizing rays cause damage to genomes, proteins, and signaling pathways that normally regulate cell activity, with harmful consequences such as accelerated aging, tumors, and cancers but also with beneficial effects in the context of radiotherapies. While the great pace of research in the twentieth century led to the identification of the molecular mechanisms for chemical lesions on the building blocks of biomacromolecules, the last two decades have brought renewed questions, for example, regarding the formation of clustered damage or the rich chemistry involving the secondary electrons produced by radiolysis. Radiation chemistry is now meeting attosecond science, providing extraordinary opportunities to unravel the very first stages of biological matter radiolysis. Read More

Annu Rev Phys Chem 2021 04 1;72:51-72. Epub 2020 Dec 1.

Program in Applied Physics, University of Michigan, Ann Arbor, Michigan 48109, USA; email:

Lateral organization in the plane of the plasma membrane is an important driver of biological processes. The past dozen years have seen increasing experimental support for the notion that lipid organization plays an important role in modulating this heterogeneity. Various biophysical mechanisms rooted in the concept of liquid-liquid phase separation have been proposed to explain diverse experimental observations of heterogeneity in model and cell membranes with distinct but overlapping applicability. Read More

Annu Rev Phys Chem 2021 04 1;72:667-691. Epub 2021 Mar 1.

Sterling Chemistry Laboratory, Yale University, New Haven, Connecticut 06520, USA; email:

The ease with which the pH is routinely determined for aqueous solutions masks the fact that the cationic product of Arrhenius acid dissolution, the hydrated proton, or H(aq), is a remarkably complex species. Here, we review how results obtained over the past 30 years in the study of H⋅(HO) cluster ions isolated in the gas phase shed light on the chemical nature of H(aq). This effort has also revealed molecular-level aspects of the Grotthuss relay mechanism for positive-charge translocation in water. Read More

Annu Rev Phys Chem 2021 04 26;72:641-666. Epub 2021 Feb 26.

Pitzer Theory Center and Department of Chemistry, University of California, Berkeley, California 94720, USA; email:

Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. Read More

Annu Rev Phys Chem 2021 04 26;72:591-616. Epub 2021 Feb 26.

Institute for Physical and Theoretical Chemistry, Goethe University Frankfurt, 60438 Frankfurt, Germany; email:

Due to the subtle interplay of site-to-site electronic couplings, exciton delocalization, nonadiabatic effects, and vibronic couplings, quantum dynamical studies are needed to elucidate the details of ultrafast photoinduced energy and charge transfer events in organic multichromophoric systems. In this vein, we review an approach that combines first-principles parameterized lattice Hamiltonians with accurate quantum dynamical simulations using advanced multiconfigurational methods. Focusing on the elementary transfer steps in organic functional materials, we address coherent exciton migration and creation of charge transfer excitons in homopolymers, notably representative of the poly(3-hexylthiophene) material, as well as exciton dissociation at polymer:fullerene heterojunctions. Read More

Annu Rev Phys Chem 2021 Apr 19;72:617-640. Epub 2021 Feb 19.

Institute of Theoretical and Computational Chemistry, Heinrich Heine University, Düsseldorf 40204, Germany; email:

This review article focuses on the understanding of intersystem crossing (ISC) in molecules. It addresses readers who are interested in the phenomenon of intercombination transitions between states of different electron spin multiplicities but are not familiar with relativistic quantum chemistry. Among the spin-dependent interaction terms that enable a crossover between states of different electron spin multiplicities, spin-orbit coupling (SOC) is by far the most important. Read More

Annu Rev Phys Chem 2021 Apr 19;72:73-97. Epub 2021 Feb 19.

Department of Mechanical Engineering, University of Minnesota, Twin Cities, Minneapolis, Minnesota 55455, USA; email:

Measurements of droplet phase and interfacial tension (IFT) are important in the fields of atmospheric aerosols and emulsion science. Bulk macroscale property measurements with similar constituents cannot capture the effect of microscopic length scales and highly curved surfaces on the transport characteristics and heterogeneous chemistry typical in these applications. Instead, microscale droplet measurements ensure properties are measured at the relevant length scale. Read More

Annu Rev Phys Chem 2021 04 12;72:565-589. Epub 2021 Feb 12.

Department of Chemistry, Osaka City University, Osaka 558-8585, Japan; email:

When an intense 1,064-nm continuous-wave laser is tightly focused at solution surfaces, it exerts an optical force on molecules, polymers, and nanoparticles (NPs). Initially, molecules and NPs are gathered into a single assembly inside the focus, and the laser is scattered and propagated through the assembly. The expanded laser further traps them at the edge of the assembly, producing a single assembly much larger than the focus along the surface. Read More

Annu Rev Phys Chem 2021 Apr 9;72:515-540. Epub 2021 Feb 9.

Department of Chemistry, University of Nevada, Reno, Nevada 89557-0216, USA; email:

In this article, we review nonadiabatic molecular dynamics (NAMD) methods for modeling spin-crossover transitions. First, we discuss different representations of electronic states employed in the grid-based and direct NAMD simulations. The nature of interstate couplings in different representations is highlighted, with the main focus on nonadiabatic and spin-orbit couplings. Read More