Annual Review of Physical Chemistry - Volume 65, 2014

The charge with the invitation to write this autobiographical article was to describe what led me to a career in science and to choose the specific topics and scientific directions I have pursued. This is thus a very personal story and by no means a scientific review of the work that is mentioned. As will be clear, this journey was not an orderly, well-thought-out plan, but just “happened,” one step after the other.

The recent development in measurement techniques and theoretical understanding has enabled us to study atmospheric vapor, cluster and nanoparticle concentrations, dynamics, and their connection to atmospheric nucleation. Here we present a summary of the chemistry of atmospheric clustering, growing nanoparticles, and their precursors. In this work, we focus particularly on atmospheric gas-to-particle conversion and recent progress in its understanding.

Multidimensional femtosecond time-resolved vibrational coherence spectroscopy allows one to investigate the evolution of vibrational coherence in electronic excited states. Methods such as pump-degenerate four-wave mixing and pump-impulsive vibrational spectroscopy combine an initial ultrashort laser pulse with a nonlinear probing sequence to reinduce vibrational coherence exclusively in the excited states. By carefully exploiting specific electronic resonances, one can detect vibrational coherence from 0 cm⁻¹ to over 2,000 cm⁻¹ and map its evolution. This review focuses on the observation and mapping of high-frequency vibrational coherence for all-trans biological polyenes such as β-carotene, lycopene, retinal, and retinal Schiff base. We discuss the role of molecular symmetry in vibrational coherence activity in the S1 electronic state and the interplay of coupling between electronic states and vibrational coherence.

Thin-film solar cells are an important source of renewable energy. The most efficient thin-film solar cells made with organic materials are blends of semiconducting polymers and fullerenes called the bulk heterojunction (BHJ). Efficient BHJs have a nanoscale phase-separated morphology that is formed during solution casting. This article reviews recent work to understand the nature of the phase-separation process resulting in the formation of the domains in polymer-fullerene BHJs. The BHJ is now viewed as a mixture of polymer-rich, fullerene-rich, and mixed polymer-fullerene domains. The formation of this structure can be understood through fundamental knowledge of polymer physics. The implications of this structure for charge transport and charge generation are given.

Crystal defects in diamond have emerged as unique objects for a variety of applications, both because they are very stable and because they have interesting optical properties. Embedded in nanocrystals, they can serve, for example, as robust single-photon sources or as fluorescent biomarkers of unlimited photostability and low cytotoxicity. The most fascinating aspect, however, is the ability of some crystal defects, most prominently the nitrogen-vacancy (NV) center, to locally detect and measure a number of physical quantities, such as magnetic and electric fields. This metrology capacity is based on the quantum mechanical interactions of the defect's spin state. In this review, we introduce the new and rapidly evolving field of nanoscale sensing based on single NV centers in diamond. We give a concise overview of the basic properties of diamond, from synthesis to electronic and magnetic properties of embedded NV centers. We describe in detail how single NV centers can be harnessed for nanoscale sensing, including the physical quantities that may be detected, expected sensitivities, and the most common measurement protocols. We conclude by highlighting a number of the diverse and exciting applications that may be enabled by these novel sensors, ranging from measurements of ion concentrations and membrane potentials to nanoscale thermometry and single-spin nuclear magnetic resonance.

Superresolution localization microscopy methods produce nanoscale images via a combination of intermittently active fluorescent probes and algorithms that can precisely determine the positions of these probes from single-molecule or few-molecule images. These algorithms vary widely in their underlying principles, complexity, and accuracy. In this review, we begin by surveying the principles of localization microscopy and describing the fundamental limits to localization precision. We then examine several different families of fluorophore localization algorithms, comparing their complexity, performance, and range of applicability (e.g., whether they require particular types of experimental information, are optimized for specific situations, or are more general). Whereas our focus is on the localization of single isotropic emitters in two dimensions, we also consider oriented dipoles, three-dimensional localization, and algorithms that can handle overlapping images of several nearby fluorophores. Throughout the review, we try to highlight practical advice for users of fluorophore localization algorithms, as well as open questions.

The photophysical behavior of organic semiconductors is governed by their excitonic states. In this review, I classify the three different exciton types (Frenkel singlet, Frenkel triplet, and charge transfer) typically encountered in organic semiconductors. Experimental challenges that arise in the study of solid-state organic systems are discussed. The steady-state spectroscopy of intermolecular delocalized Frenkel excitons is described, using crystalline tetracene as an example. I consider the problem of a localized exciton diffusing in a disordered matrix in detail, and experimental results on conjugated polymers and model systems suggest that energetic disorder leads to subdiffusive motion. Multiexciton processes such as singlet fission and triplet fusion are described, emphasizing the role of spin state coherence and magnetic fields in studying singlet ↔ triplet pair interconversion. Singlet fission provides an example of how all three types of excitons (triplet, singlet, and charge transfer) may interact to produce useful phenomena for applications such as solar energy conversion.

Computational modeling at the atomistic and mesoscopic levels has undergone dramatic development in the past 10 years to meet the challenge of adequately accounting for the many-body nature of intermolecular interactions. At the heart of this challenge is the ability to identify the strengths and specific limitations of pairwise-additive interactions, to improve classical models to explicitly account for many-body effects, and consequently to enhance their ability to describe a wider range of reference data and build confidence in their predictive capacity. However, the corresponding computational cost of these advanced classical models increases significantly enough that statistical convergence of condensed phase observables becomes more difficult to achieve. Here we review a hierarchy of potential energy surface models used in molecular simulations for systems with many degrees of freedom that best meet the trade-off between accuracy and computational speed in order to define a sweet spot for a given scientific problem of interest.

The combination of mass spectrometry and ion mobility spectrometry (IMS) employing a temperature-variable drift cell or a drift tube divided into sections to make IMS-IMS experiments possible allows information to be obtained about the molecular dynamics of polyatomic ions in the absence of a solvent. The experiments allow the investigation of structural changes of both activated and native ion populations on a timescale of 1–100 ms. Five different systems representing small and large, polar and nonpolar molecules, as well as noncovalent assemblies, are discussed in detail: a dinucleotide, a sodiated polyethylene glycol chain, the peptide bradykinin, the protein ubiquitin, and two types of peptide oligomers. Barriers to conformational interconversion can be obtained in favorable cases. In other cases, solution-like native structures can be observed, but care must be taken in the experimental protocols. The power of theoretical modeling is demonstrated.

Recent advances in high-resolution photoionization, photoelectron, and photodissociation studies based on single-photon vacuum ultraviolet (VUV) and two-color infrared (IR)-VUV, visible (Vis)-ultraviolet (UV), and VUV-VUV laser excitations are illustrated with selected examples. VUV laser photoionization coupled with velocity-map-imaging threshold photoelectron (VMI-TPE) detection can achieve comparable energy resolution but has higher-detection sensitivities than those observed in VUV laser pulsed field ionization photoelectron (PFI-PE) measurements. For molecules with known intermediate states, IR-VUV and Vis-UV excitation schemes are highly sensitive for rovibronically selected and resolved PFI-PE studies. The successful applications of the VUV-PFI-PE, VUV-VMI-TPE, and Vis-UV-PFI-PE methods to state-resolved and state-to-state photoelectron studies of transient radicals and transitional metal–containing molecules are highlighted. The most recently established VUV-VUV pump-probe time-slice VMI photoion method is shown to be promising for state-to-state photodissociation studies of small molecules relevant to planetary atmospheres and for the fundamental understanding of photodissociation dynamics.

Fluorescence fluctuation spectroscopy (FFS) techniques provide information at the single-molecule level with excellent time resolution. Usually applied at a single spot in a sample, they have been recently extended into imaging formats, referred to as imaging FFS. They provide spatial information at the optical diffraction limit and temporal information in the microsecond to millisecond range. This review provides an overview of the different modalities in which imaging FFS techniques have been implemented and discusses present imaging FFS capabilities and limitations. A combination of imaging FFS and nanoscopy would allow one to record information with the detailed spatial information of nanoscopy, which is ∼20 nm and limited only by fluorophore size and labeling density, and the time resolution of imaging FFS, limited by the fluorescence lifetime. This combination would provide new insights into biological events by providing spatiotemporal resolution at unprecedented levels.

Infrared spectroscopy has a long history as a tool for the identification of chemical compounds. More recently, various implementations of infrared spectroscopy have been successfully applied to studies of heterogeneous catalytic reactions with the objective of identifying intermediates and determining catalytic reaction mechanisms. We discuss selective applications of these techniques with a focus on several heterogeneous catalytic reactions, including hydrogenation, deNOx, water-gas shift, and reverse-water-gas shift. The utility of using isotopic substitutions and other techniques in tandem with infrared spectroscopy is discussed. We comment on the modes of implementation and the advantages and disadvantages of the various infrared techniques. We also note future trends and the role of computational calculations in such studies. The infrared techniques considered are transmission Fourier transform infrared spectroscopy, infrared reflection-absorption spectroscopy, polarization-modulation infrared reflection-absorption spectroscopy, sum-frequency generation, diffuse reflectance infrared Fourier transform spectroscopy, attenuated total reflectance, infrared emission spectroscopy, photoacoustic infrared spectroscopy, and surface-enhanced infrared absorption spectroscopy.

DNA photolyases are light-activated enzymes that repair DNA damage induced by ultraviolet (UV) radiation. UV radiation causes two of the most abundant mutagenic and cytotoxic DNA lesions: cyclobutane pyrimidine dimers and 6-4 photolesions. Photolyases selectively bind to DNA and initiate the splitting of mutagenic pyrimidine dimers via photoinduced electron transfer from a flavin adenine dinucleotide anion (FADH⁻) to the lesion triggering its repair. This review discusses the consecutive steps of the repair process, from both experimental and theoretical points of view. It covers the following issues: the process of how photolyases accommodate the lesion into their binding pockets, excitation energy transfer between two involved catalytic cofactors, photoinduced electron transfer to the lesion, the splitting of the pyrimidine dimer radical anion, and the fate of the unstable radical species created after the splitting of the thymine dimer. In particular, mechanisms of the splitting and restoration of the original bases are described in detail, and the most probable repair pathways are outlined.

Conformational changes in nucleic acids play a key role in the way genetic information is stored, transferred, and processed in living cells. Here, we describe new approaches that employ a broad range of experimental data, including NMR-derived chemical shifts and residual dipolar couplings, small-angle X-ray scattering, and computational approaches such as molecular dynamics simulations to determine ensembles of DNA and RNA at atomic resolution. We review the complementary information that can be obtained from diverse sets of data and the various methods that have been developed to combine these data with computational methods to construct ensembles and assess their uncertainty. We conclude by surveying RNA and DNA ensembles determined using these methods, highlighting the unique physical and functional insights obtained so far.

This article reviews the mechanisms through which molecules adsorbed to the surfaces of semiconductor nanocrystals, quantum dots (QDs), influence the pathways for and dynamics of intra- and interband exciton relaxation in these nanostructures. In many cases, the surface chemistry of the QDs determines the competition between Auger relaxation and electronic-to-vibrational energy transfer in the intraband cooling of hot carriers, and between electron or hole-trapping processes and radiative recombination in relaxation of band-edge excitons. The latter competition determines the photoluminescence quantum yield of the nanocrystals, which is predictable through a set of mostly phenomenological models that link the surface coverage of ligands with specific chemical properties to the rate constants for nonradiative exciton decay.

This article provides an overview of some recent advances in the modeling of photoelectron angular distributions in negative-ion photodetachment. Building on the past developments in threshold photodetachment spectroscopy that first tackled the scaling of the partial cross sections with energy, depending on the angular momentum quantum number ℓ, it examines the corresponding formulation of the central potential model and extends it to the more general case of hybrid molecular orbitals. Several conceptual approaches to understanding photoelectron angular distributions are discussed. In one approach, the angular distributions are examined based on the contributions of the symmetry-allowed s and p partial waves of the photodetached electron. In another related approach, the parent molecular orbitals are described based on their dominant s and p characters, whereas the continuum electron is described in terms of interference of the corresponding Δℓ =±1 photodetachment channels.

Quantum thermodynamics supplies a consistent description of quantum heat engines and refrigerators up to a single few-level system coupled to the environment. Once the environment is split into three (a hot, cold, and work reservoir), a heat engine can operate. The device converts the positive gain into power, with the gain obtained from population inversion between the components of the device. Reversing the operation transforms the device into a quantum refrigerator. The quantum tricycle, a device connected by three external leads to three heat reservoirs, is used as a template for engines and refrigerators. The equation of motion for the heat currents and power can be derived from first principles. Only a global description of the coupling of the device to the reservoirs is consistent with the first and second laws of thermodynamics. Optimization of the devices leads to a balanced set of parameters in which the couplings to the three reservoirs are of the same order and the external driving field is in resonance. When analyzing refrigerators, one needs to devote special attention to a dynamical version of the third law of thermodynamics. Bounds on the rate of cooling when Tc→0 are obtained by optimizing the cooling current. All refrigerators as Tc→0 show universal behavior. The dynamical version of the third law imposes restrictions on the scaling as Tc→0 of the relaxation rate γc and heat capacity cV of the cold bath.

Nanoparticles are among the most important industrial catalysts, with applications ranging from chemical manufacturing to energy conversion and storage. Heterogeneity is a general feature among these nanoparticles, with their individual differences in size, shape, and surface sites leading to variable, particle-specific catalytic activity. Assessing the activity of individual nanoparticles, preferably with subparticle resolution, is thus desired and vital to the development of efficient catalysts. It is challenging to measure the activity of single-nanoparticle catalysts, however. Several experimental approaches have been developed to monitor catalysis on single nanoparticles, including electrochemical methods, single-molecule fluorescence microscopy, surface plasmon resonance spectroscopy, X-ray microscopy, and surface-enhanced Raman spectroscopy. This review focuses on these experimental approaches, the associated methods and strategies, and selected applications in studying single-nanoparticle catalysis with chemical selectivity, sensitivity, or subparticle spatial resolution.

Sunlight can be used to drive chemical reactions to produce fuels that store energy in chemical bonds. These fuels, such as hydrogen from splitting water, have much larger energy density than do electrical storage devices. The efficient conversion of clean, sustainable solar energy using photoelectrochemical and photocatalytic systems requires precise control over the thermodynamics, kinetics, and structural aspects of materials and molecules. Generation, thermalization, trapping, interfacial transfer, and recombination of photoexcited charge carriers often occur on femtosecond to picosecond timescales. These short timescales limit the transport of photoexcited carriers to nanometer-scale distances, but nanostructures with high surface-to-volume ratios can enable both significant light absorption and high quantum efficiency. This review highlights the importance of understanding ultrafast carrier dynamics for the generation of solar fuels, including case studies on colloidal nanostructures, nanostructured photoelectrodes, and photoelectrodes sensitized with molecular chromophores and catalysts.

Nucleation is a ubiquitous phenomenon in many physical, chemical, and biological processes. In this review, we describe recent progress on the theoretical study of nucleation in polymeric fluids and soft matter, including binary mixtures (polymer blends, polymers in poor solvents, compressible polymer–small molecule mixtures), block copolymer melts, and lipid membranes. We discuss the methodological development for studying nucleation as well as novel insights and new physics obtained in the study of the nucleation behavior in these systems.