arXiv subjects

Mark A. Ratner

Publications and source records attributed to Mark A. Ratner.

At least 19 recordsLinked to original sources

arXiv2017

Thermal motions in complex liquids: the 2D Lennard-Jones liquid

Thermal motions in the 2D Lennard-Jones liquid near solidification are studied at equilibrium and under shear flow conditions. At the temperatures of the study, the liquid is significantly aggregated. On times of few to few tens of particles vibration periods, the dominant features are particles in-cage vibrations and the highest frequency longitudinal and transverse Hypersound. On time-scales of hundreds to thousands of vibration periods, the liquid appears spatially heterogeneous. On these times, slow non-oscillatory fluctuating currents persist for surprisingly long times; the hierarchical dynamics of the heterogeneous liquid results in changing temperature, density, and velocity profiles across the system. Heterogeneity fades, and a crossover to non-fluctuational Hydrodynamics is observed for smoothing times of many tens of thousands vibration periods. On these asymptotically-large times, the liquid is spatially homogeneous except for thin layers near the boundaries where the degree of crystallinity increases and the mobility decreases due to liquid-boundary interactions.

cond-mat.mes-hall↗

arXiv2017

Conductive grain systems: relaxation under strong electric fields

In an external electric field, a system of conductive grains embedded in a dielectric matrix becomes unstable and relaxes towards a conductive state. We describe and discuss the elementary acts of this relaxation. When the grains packing density is large, the relaxation is controlled by narrow gaps separating neighboring grains. The electric fields in some gaps are enhanced, relative to the external field, by the factor R/l, R being the grain radius and l the width of the gap. These enhanced fields trigger dielectric breakdown in the gaps. Both breakdown events and grain motions increase the permittivity of the composite; advancement of the breakdown process leads to global failure of insulation. The non-linear and hysteretic charge-discharge behavior of the system is determined by the main parameters characterizing the breakdown, the delay time relative to electric field increase, and the lifetime of breakdown conductivity after the supporting current has vanished.

cond-mat.soft↗

arXiv2017

Resonant Energy Transfer Under the Influence of the Evanescent Field from the Metal

We present a quantum framework based on a density matrix of a dimer system to investigate the quantum dynamics of excitation energy transfer (EET) in the presence of the evanescent field from the metal and the phonon bath. Due to the spatial correlation of the electric field in the vicinity of the metal, the spectral density of the evanescent field is similar to that of a shared phonon bath. However, the EET dynamics under the influence of the evanescent field is an open and a new problem. Here we use a thin metallic film to investigate the effect of the evanescent field on the excitation energy transfer in a dimer system based on a density matrix approach. Our results indicate that a thin metallic film enhances the energy transfer rate at the expense of absorbing energy during the process. Since the spectral density of the evanescent field is affected by the geometry of the medium and the distance of a dimer system from the medium, our results demonstrate the possibility to tune EET based on material geometry and distances. Our model also serves as an expansion to quantum heat engine model and provides a framework to investigate the EET in light harvesting molecular networks under the influence of the evanescent field.

quant-ph↗

arXiv2016

Enhancement of Resonant Energy Transfer Due to Evanescent-wave from the Metal

The high density of evanescent modes in the vicinity of a metal leads to enhancement of the near-field Förster resonant energy transfer (FRET) rate. We present a classical approach to calculate the FRET rate based on the dyadic Green's function of an arbitrary dielectric environment, and consider non-local limit of material permittivity in case of metallic halfspace and thin film. In a dimer system, we find that the FRET rate is enhanced due to shared evanescent photon modes bridging a donor and an acceptor. Furthermore, a general expression for the FRET rate for multimer systems is derived. The presence of a dielectric environment and the path interference effect enhance the transfer rate, depending on the combination of distance and geometry.

cond-mat.mes-hall↗

arXiv2015

A direct basis approach to nonorthogonality in second quantization. Theory and application

We present a direct basis formalism for using nonorthogonal basis sets in the second quantization framework. As an alternative to the dual basis formalism, a direct basis retains the Hermiticity relation between the creation and annihilation operators, with which the form of quantum operators -- e.g. the number operator and the Hamiltonian -- can be readily interpreted and manipulated. To tackle the difficulty of formulating quantum operators in the direct basis, we introduce the coefficient matrix and the generalized creation and annihilation operators, with which an arbitrary N-particle operator can be generated by simple matrix manipulations with the metric tensor of a general basis set. We illustrate the application of the direct basis formalism with the Hubbard Hamiltonian and a dynamical study with the Heisenberg equations of motion

physics.chem-ph↗

arXiv2015

On optical spectroscopy of molecular junctions

We compare theoretical techniques utilized for description of optical response in molecular junctions, and their application to simulate Raman spectroscopy in such systems. Strong and weak sides of the Hilbert vs. Liouville space, as well as quasiparticles vs. many-body states, formulations are discussed. Common origins of the methodologies and different approximations utilized in different formulations are identified.

cond-mat.mes-hall↗

arXiv2014

A non-equilibrium equation-of-motion approach to quantum transport utilizing projection operators

We consider a projection operator approach to the non-equilbrium Green function equation-of-motion (PO-NEGF EOM) method. The technique resolves problems of arbitrariness in truncation of an infinite chain of EOMs, and prevents violation of symmetry relations resulting from the truncation. The approach, originally developed by Tserkovnikov [Theor. Math. Phys. 118, 85 (1999)] for equilibrium systems, is reformulated to be applicable to time-dependent non-equilibrium situations. We derive a canonical form of EOMs, thus explicitly demonstrating a proper result for the non-equilibrium atomic limit in junction problems. A simple practical scheme applicable to quantum transport simulations is formulated. We perform numerical simulations within simple models, and compare results of the approach to other techniques, and (where available) also to exact results.

cond-mat.mes-hall↗

arXiv2013

Microphase separation as the cause of structural complexity in 2D liquids

Complex behavior in glassforming liquids is associated with formation of a mosaic of different structures. Using bond order parameters together with topological characteristics of the bond network, we show that in the mosaic of crystalline and amorphous clusters found in a 2D liquid the difference between structural sub- components translates into a difference between two coexisting phases. We suggest that the observed microphase separated mosaic is a 2D realization of what is usually invoked to explain special features found in 3D complex liquids. Conditions favoring mosaic stability are discussed; these conditions include a new type of critical behavior and long-range correlations between sub-component clusters.

cond-mat.soft↗

arXiv2013

Tunable Quantum Temperature Oscillations in Graphene and Carbon Nanoribbons

We investigate the local electron temperature distribution in carbon nano-ribbon (CNR) and graphene junctions subject to an applied thermal gradient. Using a realistic model of a scanning thermal microscope, we predict quantum temperature oscillations whose wavelength is related to that of Friedel oscillations. Experimentally, this wavelength can be tuned over several orders of magnitude by gating/doping, bringing quantum temperature oscillations within reach of the spatial resolution of existing measurement techniques.

cond-mat.mes-hall↗

arXiv2013

Single-molecule pulling: phenomenology and interpretation

Single-molecule pulling techniques have emerged as versatile tools for probing the noncovalent forces holding together the secondary and tertiary structure of macromolecules. They also constitute a way to study at the single-molecule level processes that are familiar from our macroscopic thermodynamic experience. In this Chapter, we summarize the essential phenomenology that is typically observed during single-molecule pulling, provide a general statistical mechanical framework for the interpretation of the equilibrium force spectroscopy and illustrate how to simulate single-molecule pulling experiments using molecular dynamics.

physics.bio-ph↗

arXiv2012

Polaron formation: Ehrenfest dynamics vs. exact results

We use a 1-dimensional tight binding model with an impurity site characterized by electron-vibration coupling, to describe electron transfer and localization at zero temperature, aiming to examine the process of polaron formation in this system. In particular we focus on comparing a semiclassical approach that describes nuclear motion in this many vibronic-states system on the Ehrenfest dynamics level to a numerically exact fully quantum calculation based on the Bonca-Trugman method [J. Bonča and S. A. Trugman, Phys. Rev. Lett. 75, 2566 (1995)]. In both approaches, thermal relaxation in the nuclear subspace is implemented in equivalent approximate ways: In the Ehrenfest calculation the uncoupled (to the electronic subsystem) motion of the classical (harmonic) oscillator is simply damped as would be implied by coupling to a markovian zero temperature bath. In the quantum calculation, thermal relaxation is implemented by augmenting the Liouville equation for the oscillator density matrix with kinetic terms that account for the same relaxation. In both cases we calculate the probability to trap the electron in a polaron cage and the probability that it escapes to infinity. Comparing these calculations, we find that while both result in similar long time yields for these processes, the Ehrenfest-dynamics based calculation fails to account for the correct timescale for the polaron formation. This failure results, as usual, from the fact that at the early stage of polaron formation the classical nuclear dynamics takes place on an unphysical average potential surface that reflects the otherwise-distributed electronic population in the system, while the quantum calculation accounts fully for correlations between the electronic and vibrational subsystems.

cond-mat.other↗

arXiv2012

What makes a complex liquid complex?

We view a complex liquid as a network of bonds connecting each particle to its nearest neighbors; the dynamics of this network is a chain of discrete events signaling particles rearrangements. Within this picture, we studied a two-dimensional complex liquid and found a stretched-exponential decay of the network memory and a power-law for the distribution of the times for which a particle keeps its nearest neighbors; the dependence of this distribution on temperature suggests a possible dynamical critical point. We identified and quantified the underlying spatio-temporal phenomena. The equilibrium liquid represents a hierarchical structure, a mosaic of long-living crystallites partially separated by less-ordered regions. The long-time dynamics of this structure is dominated by particles redistribution between dynamically and structurally different regions. We argue that these are generic features of locally ordered but globally disordered complex systems. In particular, these features must be taken into account by any coarse-grained theory of dynamics of complex fluids and glasses.

cond-mat.dis-nn↗

arXiv2012

Compensation of Coulomb blocking and energy transfer in the current voltage characteristic of molecular conduction junctions

We have studied the influence of both exciton effects and Coulomb repulsion on current in molecular nanojunctions. We show that dipolar energy-transfer interactions between the sites in the wire can at high voltage compensate Coulomb blocking for particular relationships between their values. Tuning this relationship may be achieved by using the effect of plasmonic nanostructure on dipolar energy transfer interactions.

cond-mat.str-el↗

arXiv2012

Yield of exciton dissociation in a donor-acceptor system

A simple model is constructed to describe dissociation of charge transfer excitons in bulk heterojunction solar cells, and its dependence on the physical parameters of the system. In bulk heterojunction organic photovoltaics (OPVs), exciton dissociation occurs almost exclusively at the interface between the donor and acceptor, following one-electron initial excitation from the HOMO to the LUMO levels of the donor, and charge transfer to the acceptor to make a charge-transfer exciton. After exciton breakup, and neglecting the trapping of individual carriers, the electron may undergo two processes for decay: one process involves the electron and/or hole leaving the interface, and migrating to the electrode. This is treated here as the electron moving on a set of acceptor sites. The second loss process is radiationless decay following recombination of the acceptor electron with the donor cation; this is treated by adding a relaxation term. These two processes compete with one another. We model both the exciton breakup and the subsequent electron motion. Results depend on tunneling amplitude, energetics, disorder, Coulomb barriers, and energy level matchups, particularly the so-called LUMO/LUMO offset.

cond-mat.str-el↗

arXiv2010

Electroluminescence spectra in weakly coupled single-molecule junctions

We have combined ab initio quantum chemistry calculations with a rate-equation formalism to analyze electroluminescence spectra in single-molecule junctions, measured recently by several groups in Scanning Tunneling Microscope setups. In our method, the entire vibrational spectrum is taken into account. Our method leads to good quantitative agreement with both the spectroscopic features of the measurements and their current and voltage dependence. Moreover, our method is able to explain several previously unexplained features. We show that in general, the quantum yield is expected to be suppressed at high bias, as is observed in one of the measurements. Additionally, we comment on the influence of the vibrational relaxation times on several features of the spectrum.

cond-mat.mes-hall↗

arXiv2010

Vibrational Excitations in Weakly Coupled Single-Molecule Junctions: A Computational Analysis

In bulk systems, molecules are routinely identified by their vibrational spectrum using Raman or infrared spectroscopy. In recent years, vibrational excitation lines have been observed in low-temperature conductance measurements on single molecule junctions and they can provide a similar means of identification. We present a method to efficiently calculate these excitation lines in weakly coupled, gateable single-molecule junctions, using a combination of ab initio density functional theory and rate equations. Our method takes transitions from excited to excited vibrational state into account by evaluating the Franck-Condon factors for an arbitrary number of vibrational quanta, and is therefore able to predict qualitatively different behaviour from calculations limited to transitions from ground state to excited vibrational state. We find that the vibrational spectrum is sensitive to the molecular contact geometry and the charge state, and that it is generally necessary to take more than one vibrational quantum into account. Quantitative comparison to previously reported measurements on pi-conjugated molecules reveals that our method is able to characterize the vibrational excitations and can be used to identify single molecules in a junction. The method is computationally feasible on commodity hardware.

cond-mat.mes-hall↗

arXiv2009

Born Oppenheimer Dynamics Near Metal Surfaces

We discuss the usefulness of Born-Oppenheimer potential surfaces for nuclear dynamics for molecules strongly coupled to metal surfaces. A simple model demonstrating the construction of such surface for a molecular junction is discussed.

cond-mat.mes-hall↗

arXiv2009

AFM pulling and the folding of donor-acceptor oligorotaxanes: phenomenology and interpretation

The thermodynamic driving force in the self-assembly of the secondary structure of a class of donor-acceptor oligorotaxanes is elucidated by means of molecular dynamics simulations of equilibrium isometric single-molecule force spectroscopy AFM experiments. The oligorotaxanes consist of cyclobis(paraquat-\emph{p}-phenylene) rings threaded onto an oligomer of 1,5-dioxynaphthalenes linked by polyethers. The simulations are performed in a high dielectric medium using MM3 as the force field. The resulting force vs. extension isotherms show a mechanically unstable region in which the molecule unfolds and, for selected extensions, blinks in the force measurements between a high-force and a low-force regime. From the force vs. extension data the molecular potential of mean force is reconstructed using the weighted histogram analysis method and decomposed into energetic and entropic contributions. The simulations indicate that the folding of the oligorotaxanes is energetically favored but entropically penalized, with the energetic contributions overcoming the entropy penalty and effectively driving the self-assembly. In addition, an analogy between the single-molecule folding/unfolding events driven by the AFM tip and the thermodynamic theory of first-order phase transitions is discussed and general conditions, on the molecule and the cantilever, for the emergence of mechanical instabilities and blinks in the force measurements in equilibrium isometric pulling experiments are presented. In particular, it is shown that the mechanical stability properties observed during the extension are intimately related to the fluctuations in the force measurements.

cond-mat.stat-mech↗