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The assembly of monomeric constituents into molecular superstructures through sequential-arrival processes has been simulated and theoretically characterized. When the energetic interactions allow for complete overlap of the particles, the model is equivalent to that of the sequential absorption of soft particles on a surface. In the present work, we consider more general cases by including arbitrary aggregating geometries and varying prescriptions of the connectivity network. The resulting theory accounts for the evolution and final-state configurations through a system of equations governing structural generation. We find that particle geometries differ significantly from those in equilibrium. In particular, variations of structural rigidity and morphology tune particle energetics and result in significant variation in the nonequilibrium distributions of the assembly in comparison to the corresponding equilibrium case. [ABSTRACT FROM AUTHOR]

Thermalized chemical reactions driven under dynamical load are characteristic of activated dynamics for arbitrary nonautonomous systems. Recent generalizations of transition state theory to obtain formally exact rates have required the construction of a time-dependent transition state trajectory. Here, we show that Lagrangian descriptors can be used to obtain this structure directly. By developing a phase space separatrix that is void of recrossings, these constructs allow for the principal criterion in the implementation of modern rate theories to be satisfied. Thus, the reactive flux over a time-varying barrier can be determined without ambiguity in chemical reactions. The generality of the formalism suggests that this approach is applicable to any activated system subjected to arbitrary driving and thermal fluctuations. [ABSTRACT FROM AUTHOR]

Chemical reactions subjected to time-varying external forces cannot generally be described through a fixed bottleneck near the transition-state barrier or dividing surface. A naive dividing surface attached to the instantaneous, but moving, barrier top also fails to be recrossing-free. We construct a moving dividing surface in phase space over a transition-state trajectory. This surface is recrossing-free for both Hamiltonian and dissipative dynamics. This is confirmed even for strongly anharmonic barriers using simulation. The power of transition-state theory is thereby applicable to chemical reactions and other activated processes even when the bottlenecks are time dependent and move across space [ABSTRACT FROM AUTHOR]

Controlling the direction and magnitude of both heat and electronic currents using rectifiers has significant implications for the advancement of molecular circuit design. In order to facilitate the implementation of new transport phenomena in such molecular structures, we examine thermal and thermoelectric rectification effects that are induced by an electron transfer process that occurs across a temperature gradient between molecules. Historically, the only known heat conduction mechanism able to generate thermal rectification in purely molecular environments is phononic heat transport. Here, we show that electron transfer between molecular sites with different local temperatures can also generate a thermal rectification effect and that electron hopping through molecular bridges connecting metal leads at different temperatures gives rise to asymmetric Seebeck effects, that is, thermoelectric rectification, in molecular junctions. [ABSTRACT FROM AUTHOR]

The persistence of a transition state structure in systems driven by time-dependent environments allows the application of modern reaction rate theories to solution-phase and nonequilibrium chemical reactions. However, identifying this structure is problematic in driven systems and has been limited by theories built on series expansion about a saddle point. Recently, it has been shown that to obtain formally exact rates for reactions in thermal environments, a transition state trajectory must be constructed. Here, using optimized Lagrangian descriptors [G. T. Craven and R. Hernandez, Phys. Rev. Lett. 115, 148301 (2015)], we obtain this so-called distinguished trajectory and the associated moving reaction manifolds on model energy surfaces subject to various driving and dissipative conditions. In particular, we demonstrate that this is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions. The development of these objects is paramount in the theory of reaction dynamics as the transition state structure and its underlying network of manifolds directly dictate reactivity and selectivity. [ABSTRACT FROM AUTHOR]

A theory is developed to describe the coupled transport of energy and charge in networks of electron donor-acceptor sites which are seated in a thermally heterogeneous environment, where the transfer kinetics are dominated by Marcus-type hopping rates. It is found that the coupling of heat and charge transfer in such systems gives rise to exotic transport phenomena which are absent in thermally homogeneous systems and cannot be described by standard thermoelectric relations. Specifically, the directionality and extent of thermal transistor amplification and cyclical electronic currents in a given network can be controlled by tuning the underlying temperature gradient in the system. The application of these findings toward the optimal control of multithermal currents is illustrated on a paradigmatic nanostructure. [ABSTRACT FROM AUTHOR]

Energy transport is a fundamental physical process that plays a prominent role in the function and performance of myriad systems and technologies. Recent experimental measurements have shown that subjecting a macroscale system to a time-periodic temperature gradient can increase thermal conductivity in comparison to a static temperature gradient. Here, we theoretically examine this mechanism in a nanoscale model by applying a stochastic Langevin framework to describe the energy transport properties of a particle connecting two heat baths with different temperatures, where the temperature difference between baths is oscillating in time. Analytical expressions for the energy flux of each heat bath and for the system itself are derived for the case of a free particle and a particle in a harmonic potential. We find that dynamical effects in the energy flux induced by temperature oscillations give rise to complex energy transport hysteresis effects. The presented results suggest that applying time-periodic temperature modulations is a potential route to control energy storage and release in molecular devices and nanosystems.