▪ Abstract Electron transmission through molecules and molecular interfaces has been a subject of intensive research due to recent interest in electron-transfer phenomena underlying the operation of the scanning-tunneling microscope on one hand, and in the transmission properties of molecular bridges between conducting leads on the other. In these processes, the traditional molecular view of electron transfer between donor and acceptor species gives rise to a novel view of the molecule as a current-carrying conductor, and observables such as electron-transfer rates and yields are replaced by the conductivities, or more generally by current-voltage relationships, in molecular junctions. Such investigations of electrical junctions, in which single molecules or small molecular assemblies operate as conductors, constitute a major part of the active field of molecular electronics. In this article I review the current knowledge and understanding of this field, with particular emphasis on theoretical issues. Different approaches to computing the conduction properties of molecules and molecular assemblies are reviewed, and the relationships between them are discussed. Following a detailed discussion of static-junctions models, a review of our current understanding of the role played by inelastic processes, dephasing and thermal-relaxation effects is provided. The most important molecular environment for electron transfer and transmission is water, and our current theoretical understanding of electron transmission through water layers is reviewed. Finally, a brief discussion of overbarrier transmission, exemplified by photoemission through adsorbed molecular layers or low-energy electron transmission through such layers, is provided. Similarities and differences between the different systems studied are discussed.

Stable molecular switches: Many single-molecule current switches have been reported, but most show poor stability because of weak contacts to metal electrodes. Jia et al. covalently bonded a diarylethene molecule to graphene electrodes and achieved stable photoswitching at room temperature (see the Perspective by Frisbie). The incorporation of short bridging alkyl chains between the molecule and graphene decoupled their pielectron systems and allowed fast conversion of the open and closed ring states. Science , this issue p. 1443 ; see also p. 1394

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. Section 2 provides an overview of the key experimental observations of these effects, while Section 3 describes our current theoretical understanding of the effect of strong light–matter coupling on chemical dynamics. A brief outline of applications to energy conversion processes is given in Section 4. Pending technical issues in the construction of theoretical approaches are briefly described in Section 5. Finally, the summary in Section 6 outlines the paths ahead in this exciting endeavor.

Recent experiments suggest that vibrational strong coupling (VSC) may significantly modify ground-state chemical reactions and their rates even without external pumping. The intrinsic mechanism of this “vacuum-field catalysis” remains largely unclear. Generally, modifications of thermal reactions in the ground electronic states can be caused by equilibrium or non-equilibrium effects. The former are associated with modifications of the reactant equilibrium distribution as expressed by the transition state theory of chemical reaction rates, while the latter stem from the dynamics of reaching and leaving transition state configurations. Here, we examine how VSC can affect chemical reactions rates in a cavity environment according to transition state theory. Our approach is to examine the effect of coupling to cavity mode(s) on the potential of mean force (PMF) associated with the reaction coordinate. Within the context of classical nuclei and classical photons and also assuming no charge overlap between molecules, we find that while the PMF can be affected by the cavity environment, this effect is negligible for the usual micron-length cavities used to examine VSC situations.

We simulate vibrational strong coupling (VSC) and vibrational ultrastrong coupling (V-USC) for liquid water with classical molecular dynamics simulations. When the cavity modes are resonantly coupled to the O−H stretch mode of liquid water, the infrared spectrum shows asymmetric Rabi splitting. The lower polariton (LP) may be suppressed or enhanced relative to the upper polariton (UP) depending on the frequency of the cavity mode. Moreover, although the static properties and the translational diffusion of water are not changed under VSC or V-USC, we do find the modification of the orientational autocorrelation function of H₂O molecules especially under V-USC, which could play a role in ground-state chemistry. Significance Strong coupling between a vibrational molecular peak and a cavity mode is known to lead to interesting spectroscopic features and even the modification of ground-state chemistry from small molecules to enzyme. Here, we develop a simulation tool for modeling such vibrational strong (and ultrastrong) coupling at the interface between optics, chemistry, and biology. With liquid water as an example, our simulation not only reveals an asymmetric Rabi splitting in the infrared spectrum, but also captures cavity modification of the dynamic properties of water.

A rate constant expression for charge transfer reactions mediated by flexible bridges is presented as a series of terms of decreasing importance. The leading term corresponds to the static limit obtained from the Condon approximation. Corrections due to finite time fluctuations are evaluated explicitly, assuming a Gaussian shape of the coupling autocorrelation function and the Marcus model with a one-dimensional harmonic thermal bath. The use of this model for the interpretation of experimental data and the expected magnitudes of the fluctuation effects are discussed.