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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 Apr;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 Apr 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 Apr 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 Apr 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 Apr 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 Apr 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

Annu Rev Phys Chem 2021 Apr 9;72:489-513. Epub 2021 Feb 9.

Dipartimento di Chimica e Chimica Industriale, Università di Pisa, 56124 Pisa, Italy; email:

Multiscale models combining quantum mechanical and classical descriptions are a very popular strategy to simulate properties and processes of complex systems. Many alternative formulations have been developed, and they are now available in all of the most widely used quantum chemistry packages. Their application to the study of light-driven processes, however, is more recent, and some methodological and numerical problems have yet to be solved. Read More

Annu Rev Phys Chem 2021 Apr 27;72:399-421. Epub 2021 Jan 27.

Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409, USA; email:

The Born-Oppenheimer potential energy surface (PES) has come a long way since its introduction in the 1920s, both conceptually and in predictive power for practical applications. Nevertheless, nearly 100 years later-despite astonishing advances in computational power-the state-of-the-art first-principles prediction of observables related to spectroscopy and scattering dynamics is surprisingly limited. For example, the water dimer, (HO), with only six nuclei and 20 electrons, still presents a formidable challenge for full-dimensional variational calculations of bound states and is considered out of reach for rigorous scattering calculations. Read More

Annu Rev Phys Chem 2021 Apr 27;72:467-488. Epub 2021 Jan 27.

Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA; email:

Enzyme cascades are plentiful in nature, but they also have potential in artificial applications due to the possibility of using the target substrate in biofuel cells, electrosynthesis, and biosensors. Cascade reactions from enzymes or hybrid bioorganic catalyst systems exhibit extended substrate range, reaction depth, and increased overall performance. This review addresses the strategies of cascade biocatalysis and bioelectrocatalysis for () CO fixation, () high value-added product formation, () sustainable energy sources via deep oxidation, and () cascaded electrochemical enzymatic biosensors. Read More

Annu Rev Phys Chem 2021 Apr 27;72:35-50. Epub 2021 Jan 27.

Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom; email:

I describe some of the science that I have been involved in during the last 60 years and the changes in equipment that made it possible. Starting with an interest in spectroscopy and measurement of NMR parameters, I moved to work on theoretical aspects of spin systems and infrared and Raman line shapes. This morphed into using the new technique of computer simulation to study such problems. Read More

Annu Rev Phys Chem 2021 Apr 25;72:353-373. Epub 2021 Jan 25.

Department of Chemistry, University of Oxford, Oxford OX1 3QZ, United Kingdom; email:

Since external magnetic fields were first employed to deflect paramagnetic atoms in 1921, a range of magnetic field-based methods have been introduced to state-selectively manipulate paramagnetic species. These methods include magnetic guides, which selectively filter paramagnetic species from all other components of a beam, and magnetic traps, where paramagnetic species can be spatially confined for extended periods of time. However, many of these techniques were developed for atomic-rather than molecular-paramagnetic species. Read More

Annu Rev Phys Chem 2021 Apr 22;72:423-443. Epub 2021 Jan 22.

Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA; email:

Because plasmonic metal nanostructures combine strong light absorption with catalytically active surfaces, they have become platforms for the light-assisted catalysis of chemical reactions. The enhancement of reaction rates by plasmonic excitation has been extensively discussed. This review focuses on a less discussed aspect: the induction of new reaction pathways by light excitation. Read More

Annu Rev Phys Chem 2021 Apr 20;72:375-397. Epub 2021 Jan 20.

Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA; email:

Aerosols are liquid or solid particles suspended in the atmosphere, typically with diameters on the order of nanometers to microns. These particles impact air quality and the radiative balance of the planet. Dry deposition is a key process for the removal of aerosols from the atmosphere and plays an important role in controlling the lifetime of atmospheric aerosols. Read More

Annu Rev Phys Chem 2021 Apr 20;72:331-351. Epub 2021 Jan 20.

State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, iChEM, College of Energy, Xiamen University, Xiamen 361005, China; email:

As energy demands increase, electrocatalysis serves as a vital tool in energy conversion. Elucidating electrocatalytic mechanisms using in situ spectroscopic characterization techniques can provide experimental guidance for preparing high-efficiency electrocatalysts. Surface-enhanced Raman spectroscopy (SERS) can provide rich spectral information for ultratrace surface species and is extremely well suited to studying their activity. Read More

Annu Rev Phys Chem 2021 Apr 13;72:307-329. Epub 2021 Jan 13.

Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA; email:

Mass spectrometry imaging (MSI) is a powerful, label-free technique that provides detailed maps of hundreds of molecules in complex samples with high sensitivity and subcellular spatial resolution. Accurate quantification in MSI relies on a detailed understanding of matrix effects associated with the ionization process along with evaluation of the extraction efficiency and mass-dependent ion losses occurring in the analysis step. We present a critical summary of approaches developed for quantitative MSI of metabolites, lipids, and proteins in biological tissues and discuss their current and future applications. Read More

Annu Rev Phys Chem 2021 Apr 13;72:279-306. Epub 2021 Jan 13.

Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, USA; email:

In this review, we discuss the recent developments and applications of vibrational sum-frequency generation (VSFG) microscopy. This hyperspectral imaging technique can resolve systems without inversion symmetry, such as surfaces, interfaces and noncentrosymmetric self-assembled materials, in the spatial, temporal, and spectral domains. We discuss two common VSFG microscopy geometries: wide-field and confocal point-scanning. Read More

Annu Rev Phys Chem 2021 Apr 13;72:253-278. Epub 2021 Jan 13.

Department of Chemistry, Stanford University, Stanford, California 94305, USA; email:

We review the emerging method of super-resolved cryogenic correlative light and electron microscopy (srCryoCLEM). Super-resolution (SR) fluorescence microscopy and cryogenic electron tomography (CET) are both powerful techniques for observing subcellular organization, but each approach has unique limitations. The combination of the two brings the single-molecule sensitivity and specificity of SR to the detailed cellular context and molecular scale resolution of CET. Read More

Annu Rev Phys Chem 2021 Apr 1;72:235-252. Epub 2021 Nov 1.

Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA; email:

Atmospheric aerosols are suspended particulate matter of varying composition, size, and mixing state. Challenges remain in understanding the impact of aerosols on the climate, atmosphere, and human health. The effect of aerosols depends on their physicochemical properties, such as their hygroscopicity, phase state, and surface tension. Read More

Annu Rev Phys Chem 2021 Apr 1;72:213-234. Epub 2021 May 1.

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China; email:

Revealing the intrinsic relationships between the structure, properties, and performance of the electrochemical interface is a long-term goal in the electrochemistry and surface science communities because it could facilitate the rational design of electrochemical devices. Achieving this goal requires in situ characterization techniques that provide rich chemical information and high spatial resolution. Electrochemical tip-enhanced Raman spectroscopy (EC-TERS), which provides molecular fingerprint information with nanometer-scale spatial resolution, is a promising technique for achieving this goal. Read More

Annu Rev Phys Chem 2021 Apr 4;72:165-188. Epub 2021 Jan 4.

Department of Chemistry and Chemical Biology, University of California, Merced, California 95343, USA; email:

Including both environmental and vibronic effects is important for accurate simulation of optical spectra, but combining these effects remains computationally challenging. We outline two approaches that consider both the explicit atomistic environment and the vibronic transitions. Both phenomena are responsible for spectral shapes in linear spectroscopy and the electronic evolution measured in nonlinear spectroscopy. Read More

Annu Rev Phys Chem 2021 Apr 4;72:189-212. Epub 2021 Jan 4.

Physicochimie des Électrolytes et Nanosystèmes Interfaciaux, CNRS 8234, Sorbonne Université, F-75005 Paris, France; email:

Many key industrial processes, from electricity production, conversion, and storage to electrocatalysis or electrochemistry in general, rely on physical mechanisms occurring at the interface between a metallic electrode and an electrolyte solution, summarized by the concept of an electric double layer, with the accumulation/depletion of electrons on the metal side and of ions on the liquid side. While electrostatic interactions play an essential role in the structure, thermodynamics, dynamics, and reactivity of electrode-electrolyte interfaces, these properties also crucially depend on the nature of the ions and solvent, as well as that of the metal itself. Such interfaces pose many challenges for modeling because they are a place where quantum chemistry meets statistical physics. Read More

Annu Rev Phys Chem 2021 Apr 15;72:143-163. Epub 2020 Dec 15.

Department of Molecular Biology and Biochemistry, University of California, Irvine, California 92697, USA; email:

α-Crystallins are small heat-shock proteins that act as holdase chaperones. In humans, αA-crystallin is expressed only in the eye lens, while αB-crystallin is found in many tissues. α-Crystallins have a central domain flanked by flexible extensions and form dynamic, heterogeneous oligomers. Read More

Annu Rev Phys Chem 2021 Apr 9;72:121-142. Epub 2020 Dec 9.

Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA; email:

Understanding the excited-state dynamics of nanomaterials is essential to their applications in photoenergy storage and conversion. This review summarizes recent progress in the excited-state dynamics of atomically precise gold (Au) nanoclusters (NCs). We first discuss the electronic structure and typical relaxation pathways of Au NCs from subpicoseconds to microseconds. Read More

Annu Rev Phys Chem 2021 Apr 4;72:1-34. Epub 2021 Dec 4.

The Fritz Haber Research Center and Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel; email:

This is the story of a career in theoretical chemistry during a time of dramatic changes in the field due to phenomenal growth in the availability of computational power. It is likewise the story of the highly gifted graduate students and postdoctoral fellows that I was fortunate to mentor throughout my career. It includes reminiscences of the great mentors that I had and of the exciting collaborations with both experimentalists and theorists on which I built much of my research. Read More

Annu Rev Phys Chem 2021 Apr 2;72:99-119. Epub 2021 Dec 2.

Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, Los Angeles, California 90095, USA; email:

The size- and shape-controlled enhanced optical response of metal nanoparticles (NPs) is referred to as a localized surface plasmon resonance (LSPR). LSPRs result in amplified surface and interparticle electric fields, which then enhance light absorption of the molecules or other materials coupled to the metallic NPs and/or generate hot carriers within the NPs themselves. When mediated by metallic NPs, photocatalysis can take advantage of this unique optical phenomenon. Read More

Annu Rev Phys Chem 2020 Apr;71:415-433

Department of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.

At the intersection of spectroscopy and microscopy lie techniques that are capable of providing subnanometer imaging of excited states of individual molecules or nanoparticles. Such approaches are particularly important for imaging macromolecules or nanoparticles large enough to have a high probability of containing a defect. These inevitable defects often control properties and function despite an otherwise ideal structure. Read More