"Hot" electrons in metallic nanostructures -- non-thermal carriers or heating?

Understanding the interplay between illumination and the electron distribution in metallic nanostructures is a crucial step towards developing applications such as plasmonic photo-catalysis for green fuels, nano-scale photo-detection and more. Elucidating this interplay is challenging, as it requires taking into account all channels of energy flow in the electronic system. Here, we develop such a theory, which is based on a coupled Boltzmann-heat equations and requires only energy conservation and basic thermodynamics, where the electron distribution, and the electron and phonon (lattice) temperatures are determined {\em uniquely}. Applying this theory to realistic illuminated nanoparticle systems, we find that the electron and phonon temperatures are similar, thus justifying the (classical) single temperature models. We show that while the fraction of high-energy ``hot'' carriers compared to thermalized carriers grows substantially with illumination intensity, it remains extremely small (on the order of $10^{-8}$). Importantly, most of the absorbed illumination power goes into heating rather than generating hot carriers, thus rendering plasmonic hot carrier generation extremely inefficient. Our formulation allows for the first time a unique quantitative comparison of theory and measurements of steady-state electron distributions in metallic nanostructures.Comment: includes complete answers to claims raised in arXiv:1906.06599 on previous versions of this documen

Dynamical coupling and negative differential resistance from interactions across the molecule-electrode interface in molecular junctions

Negative differential resistance - a decrease in current with increasing bias voltage - is a counter-intuitive effect that is observed in various molecular junctions. Here, we present a novel mechanism that may be responsible for such an effect, based on strong Coulomb interaction between electrons in the molecule and electrons on the atoms closest to the molecule. The Coulomb interaction induces electron-hole binding across the molecule-electrode interface, resulting in a renormalized and enhanced molecule-electrode coupling. Using a self-consistent non-equilibrium Green's function approach, we show that the effective coupling is non-monotonic in bias voltage, leading to negative differential resistance. The model is in accord with recent experimental observations that showed a correlation between the negative differential resistance and the coupling strength. We provide detailed suggestions for experimental tests which may help to shed light on the origin of the negative differential resistance. Finally, we demonstrate that the interface Coulomb interaction affects not only the I-V curves but also the thermoelectric properties of molecular junctions

Origin of thermoelectric response fluctuations in single-molecule junctions

The thermoelectric response of molecular junctions exhibits large fluctuations, as observed in recent experiments [e.g. Malen J. A. {\sl et al.}, Nano Lett. {\bf 10}, 3406 (2009)]. These were attributed to fluctuations in the energy alignment between the highest occupied molecular orbital (HOMO) and the Fermi level at the electrodes. By analyzing these fluctuations assuming resonant transport through the HOMO level, we demonstrate that fluctuations in the HOMO level alone cannot account for the observed fluctuations in the thermopower, and that the thermo-voltage distributions obtained using the most common method, the Non-equilibrium Green's function method, are qualitatively different than those observed experimentally. We argue that this inconsistency between the theory and experiment is due to the level broadening, which is inherently built-in to the method, and smears out any variations of the transmission on energy scales smaller than the level broadening. We show that although this smearing only weakly affects the transmission, it has a large effect on the calculated thermopower. Using the theory of open quantum systems we account for both the magnitude of the variations and the qualitative form of the distributions, and show that they arise not only from variations in the HOMO-Fermi level offset, but also from variations of the local density of states at the contact point between the molecule and the electrode

Transport Through Self-Assembled Monolayer Molecular Junctions: Role of In-Plane Dephasing

Self-assembled-monolayer (SAM) molecular junctions (MJs) constitute a promising building block candidate for future molecular electronic devices. Transport properties of SAM-MJs are usually calculate using either the phenomenological Simmons model, or a fully-coherent transport theory, employing the SAMs periodicity. We suggest that dephasing plays an important role in determining the transport properties of SAM-MJs. We present an approach for calculating the transport properties of SAM-MJs that inherently takes into account in-plane dephasing in the electron motion as it traverses the SAM plane. The calculation is based on the non-equilibrium Green's function formalism, with a local dynamics approximation that describes incoherent motion along the SAM plane. Our approach describes well the two hallmarks of transport through SAM-MJs, namely the exponential decay of current with molecular chain length and the reduction of the current per molecule as compared to single-molecule junctions. Specifically, we show that dephasing leads to an exponential decay of the current as a function of molecular length, even for resonant tunneling, where the fully coherent calculation shows little or no length-dependence of the current. The dephasing is also shown to lead to a substantial reduction of the current in a SAM-MJ as compared to the single molecule junction, in a realistic parameter regime, where the coherent calculation shows only a very small reduction of the current. Finally, we discuss the effect of dephasing on more subtle transport phenomena such as the conductance even-odd effect and negative differential resistance.Comment: 10 pages, 7 figures, accepted to J. Phys. Chem.

Quantum transport under AC drive from the leads : A Quantum Master Equation approach

Evaluating the time-dependent dynamics of driven open quantum systems is relevant for a theoretical description of many systems, including molecular junctions, quantum dots, cavity-QED experiments, cold atoms experiments and more. Here, we formulate a rigorous microscopic theory of an out-of-equilibrium open quantum system of non-interacting particles on a lattice weakly coupled to multiple baths and driven by periodically varying thermodynamic parameters like temperature and chemical potential of the bath. The particles can be either bosonic or fermionic and the lattice can be of any dimension and geometry. Based on Redfield quantum master equation under Born-Markov approximation, we derive a complete set of linear differential equations for equal time two-point correlation functions from which various physical observables, for example, current, can be calculated. Various interesting physical effects, such as resonance, can be directly read-off from the equations. Thus, our theory is quite general gives quite transparent and easy-to-calculate results. We validate our theory by comparing with exact numerical simulations. We apply our method to a generic open quantum system, namely a double-quantum dot coupled to leads with modulating chemical potentials. Two most important experimentally relevant insights from this are : (i) time-dependent measurements of current for symmetric oscillating voltages (with zero instantaneous voltage bias) can point to the degree of asymmetry in the system, and (ii) under certain conditions, time-dependent currents can exceed time-averaged currents by several orders of magnitude, and can therefore be detected even when the average current is below the measurement threshold

Thermal effects - an alternative mechanism for plasmonic-assisted photo-catalysis

Recent experiments claimed that the enhancement of catalytic reaction rates occurs via the reduction of activation barriers driven by non-equilibrium (``hot'') electrons in plasmonic metal nanoparticles. These experiments place plasmonic photo-catalysis as a promising path for enhancing the efficiency of various chemical reactions. Here, we argue that what appears to be photo-catalysis is in fact thermo-catalysis, driven by the well-known plasmon-enhanced ability of illuminated metallic nanoparticles to serve as heat sources. Specifically, we point to some of the most important papers in the field, and show that a simple theory of illumination-induced heating can explain the extracted experimental data to remarkable agreement, with minimal to no fit parameters. We further show that any small temperature difference between the photocatalysis experiment and a control experiment performed under uniform external heating is effectively amplified by the exponential sensitivity of the reaction, and very likely to be interpreted incorrectly as ``hot'' electron effects

Phonon as environmental disturbance in three level system

This work investigates the effect of phonon coupling on the transfer of population and creation of coherence using variant of stimulated Raman adiabatic passage (STIRAP) known as \emph{fractional} stimulated Raman adiabatic passage (FSTIRAP). The study is based on the Liouville equation, which is solved numerically in the adiabatic limit. Although the phonon is assumed to be coupled only to the intermediate state, it is coupled to the other two states by dipolar system-environment interaction, inducing phonon coupling to the other states which are not directly in contact with the phonon. At zero temperature the STIRAP pulse protocol's efficiency of the transfer decreases exponentially with the electron-phonon coupling, until the coupling strength is strong enough to make the process fully incoherent, in which case the population transfer is $\frac{1}{3}$ in each level. For the FSTIRAP protocol we find that the transferred population to target state decreases, leaving some population on the intermediate state. Consequently, there is an increase in the magnitude of the coherences $\rho_{01}, \rho_{12}$, albeit small. Furthermore population transfer for non-zero temperature and effect of coupling strength is investigated, it is observed that while both parameters negatively influence the efficiency of transfer the former decrease the transfer exponentially, thereby equilibrating the system fast, while the latter seen to decrease the transfer monotonically, and hence equilibrates slowly

Optical Flip-Flops and Shift Registers from populations and coherences in multi-level systems using stimulated Raman adiabatic passage

In digital circuits, a Flip-Flop (FF) is a circuit element that has two stable states which can be used to store and remember state information. The state of the circuit can be changed by applying signals to the control input. FFs are the basic building blocks of sequential logic circuits, as logic gates AND,OR, NOT are the basic building block for combinational logic circuits, and are therefore necessary for any computations involving memory. Consequently, the design and implementation of FFs can be considered as a pre-requisite for memory machine design. Here we present the design of an optical FFs in an atomic multi-level system, based on the optical manipulation of populations and coherences using stimulated Raman adiabatic passage. We first demonstrate that both populations and coherences can be transferred over multistate systems. We then propose the design of toggle-FFs, Delay-FFs, and Serial-in Serial-Out (SISO) shift registers using such systems. For the design of the filp-flops we use a three level $\Lambda$-type system. In order to design SISO shift registers we concatenate two $\Lambda$-type systems and construct an "M"-type scheme, and similarly concatenating three $\Lambda$-type system we are able to obtain a seven level system. By concatenating we are able to use output of one three level $\Lambda$-type system serve as input of another three level $\Lambda$-type system. On top of using populations for design of logic gates, we uniquely exploit the coherences for logic machine, which provides an additional degree of freedom which can be used for the design of computing elements

Maintaining the local temperature below the critical value in thermally out of equilibrium superconducting wires

A generalized theory of open quantum systems combined with mean-field theory is used to study a superconducting wire in contact with thermal baths at different temperatures. It is shown that, depending on the temperature of the colder bath, the temperature of the hotter bath can greatly exceed the equilibrium critical temperature, and still the local temperature in the wire is maintained below the critical temperature and hence the wire remains in the superconducting state. The effects of contact areas and disorder are studied. Finally, an experimental setup is suggested to test our predictions.Comment: 4+ pages, 3 figrues; also http://www.newscientist.com/article/mg20427365.400-superconductors-can-come-i\n-from-the-cold.htm

Energy flow and thermo-electricity in atomic and molecular junctions

Advances in the fabrication and characterization of nanoscale systems now allow for a deeper understanding of one of the most basic issues in science and technology: the flow of energy at the microscopic level. In this Colloquium we survey recent advances and present understanding of physical mechanisms of energy transport in nanostructures, focusing mainly on molecular junctions and atomic wires. We examine basic issues such as thermal conductivity, thermoelectricity, local temperature and heating, and the relation between energy current density and temperature gradient - known as Fourier's law. We critically report on both theoretical and experimental progress in each of these issues, and discuss future research opportunities in the field.Comment: 28 pages, 10 figures. Final version, accepted to RM