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Kirill A. Velizhanin

Publications and source records attributed to Kirill A. Velizhanin.

At least 19 recordsLinked to original sources
arXiv2022

Kinetics of Carbon Condensation in Detonation of High Explosives: First-Order Phase Transition Theory Perspective

The kinetics of carbon condensation, or carbon clustering, in detonation of carbon-rich high explosives is modeled by solving a system of rate equations for concentrations of carbon particles. Unlike previous efforts, the rate equations account not only for the aggregation of particles, but also for their fragmentation in a thermodynamically consistent manner. Numerical simulations are performed, yielding the distribution of particle concentrations as a function of time. In addition to that, analytical expressions are obtained for all the distinct steps and regimes of the condensation kinetics, which facilitates the analysis of the numerical results and allows one to study the sensitivity of the kinetic behavior to the variation of system parameters. The latter is important because the numerical values of many parameters are not reliably known at present. The theory of the kinetics of first-order phase transitions is found adequate to describe the general kinetic trends of carbon condensation, as described by the rate equations. Such physical phenomena and processes as the coagulation, nucleation, growth, and Ostwald ripening are observed and their dependence on various system parameters is studied and reported. It is believed that the present work will become useful when analyzing the present and future results for the kinetics of carbon condensation, obtained from experiments or atomistic simulations.

physics.chem-ph↗
arXiv2020

Rigorous Analysis of Non-Ideal Solubility of Sodium and Copper Chlorides in Water Vapor Using Pitzer-Pabalan Model

Gaseous mixtures of water vapor and neutral molecules of salt (e.g., NaCl, CuCl etc.) can be highly non-ideal due to the strong attractive interaction between salt and water molecules. In particular, this can result in high solubility of salts in water vapor and a strong dependence of solubility on vapor pressure. The analysis of salt solubility in water vapor can be done using the Pitzer-Pabalan model, which is based on the thermodynamic theory of imperfect gases. The original Pitzer-Pabalan work demonstrated that one can reproduce experimental data for NaCl solubility in vapor. No analysis was performed on the reliability of their original fits, which we believe has contributed to the lack of applications of the Pitzer-Pabalan model despite the apparent success of the original paper. In this work, we report recent progress in developing a rigorous fitting procedure to parameterize the Pitzer-Pabalan model using experimental data. Specifically, we performed fitting of the experimental results obtained elsewhere for NaCl and CuCl. We investigate the degree of underfitting/overfitting and the sensitivity of the fitting quality to variations in the resulting fitting parameters. The results, as represented by the thermodynamic parameters describing the energetics of formation of salt-bearing water clusters, were successfully benchmarked against Gaussian 16 ab initio quantum chemistry calculations. The resulting rigorous fitting procedure presented here can now be applied to other systems.

physics.chem-ph↗
arXiv2019

Topology, Landscapes, and Biomolecular Energy Transport

While ubiquitous, energy redistribution remains a poorly understood facet of the nonequilibrium thermodynamics of biomolecules. At the molecular level, finite-size effects, pronounced nonlinearities, and ballistic processes produce behavior that diverges from the macroscale. Here, we show that transient thermal transport reflects macromolecular energy landscape architecture through the topological characteristics of molecular contacts and the nonlinear processes that mediate dynamics. While the former determines transport pathways via pairwise interactions, the latter reflects frustration within the landscape for local conformational rearrangements. Unlike transport through small-molecule systems, such as alkanes, nonlinearity dominates over coherent processes at even quite short time- and length-scales. Our exhaustive all-atom simulations and novel local-in-time and space analysis, applicable to both theory and experiment, permit dissection of energy migration in biomolecules. The approach demonstrates that vibrational energy transport can probe otherwise inaccessible aspects of macromolecular dynamics and interactions that underly biological function.

physics.bio-ph↗
arXiv2019

Exciton Relaxation in Carbon Nanotubes via Electronic-to-Vibrational Energy Transfer

Covalent functionalization of semiconducting single-wall carbon nanotubes (CNT) introduces new photoluminescent emitting states. Theses states are spatially localized at around functionalization sites and strongly red-shifted relative to the emission commonly observed from the nanotube band-edge exciton state. A particularly important feature of these localized exciton states is that, because the exciton is no longer free to diffusively sample photoluminescent quenching sites along the CNT length, its lifetime is significantly extended. We have recently demonstrated that an important relaxation channel of such localized excitons is the electronic-to-vibrational energy transfer (EVET). This process is analogous to the Förster resonance energy transfer (FRET) except the final state of this process is not electronically, but vibrationally excited molecules of the surrounding medium (e.g., solvent). In this work we develop the general theory of EVET, and apply it to the specific case of EVET-mediated relaxation of defect-localized excitons in covalently functionalized CNT. The resulting EVET relaxation times are in good agreement with experimental data.

cond-mat.mes-hall↗
arXiv2018

A Spin-1 Representation for Dual-Funnel Energy Landscapes

The interconversion between left- and right-handed helical folds of a polypeptide defines a dual-funneled free energy landscape. In this context, the funnel minima are connected through a continuum of unfolded conformations, evocative of the classical helix-coil transition. Physical intuition and recent conjectures suggest that this landscape can be mapped by assigning a left- or right-handed helical state to each residue. We explore this possibility using all-atom replica exchange molecular dynamics and an Ising-like model, demonstrating that the energy landscape architecture is at odds with a two-state picture. A three-state model - left, right, and unstructured - can account for most key intermediates during chiral interconversion. Competing folds and excited conformational states still impose limitations on the scope of this approach. However, the improvement is stark: Moving from a two-state to a three-state model decreases the fit error from 1.6 $k_B T$ to 0.3 $k_B T$ along the left-to-right interconversion pathway.

cond-mat.soft↗
arXiv2018

Topological quantization of energy transport in micro- and nano-mechanical lattices

Topological effects typically discussed in the context of quantum physics are emerging as one of the central paradigms of physics. Here, we demonstrate the role of topology in energy transport through dimerized micro- and nano-mechanical lattices in the classical regime, i.e., essentially "masses and springs". We show that the thermal conductance factorizes into topological and non-topological components. The former takes on three discrete values and arises due to the appearance of edge modes that prevent good contact between the heat reservoirs and the bulk, giving a length-independent reduction of the conductance. In essence, energy input at the boundary mostly stays there, an effect robust against disorder and nonlinearity. These results bridge two seemingly disconnected disciplines of physics, namely topology and thermal transport, and suggest ways to engineer thermal contacts, opening a direction to explore the ramifications of topological properties on nanoscale technology.

cond-mat.mes-hall↗
arXiv2018

Magneto-Optics of Exciton Rydberg States in a Monolayer Semiconductor

We report 65 tesla magneto-absorption spectroscopy of exciton Rydberg states in the archetypal monolayer semiconductor WSe$_2$. The strongly field-dependent and distinct energy shifts of the 2s, 3s, and 4s excited neutral excitons permits their unambiguous identification and allows for quantitative comparison with leading theoretical models. Both the sizes (via low-field diamagnetic shifts) and the energies of the $ns$ exciton states agree remarkably well with detailed numerical simulations using the non-hydrogenic screened Keldysh potential for 2D semiconductors. Moreover, at the highest magnetic fields the nearly-linear diamagnetic shifts of the weakly-bound 3s and 4s excitons provide a direct experimental measure of the exciton's reduced mass, $m_r = 0.20 \pm 0.01~m_0$.

cond-mat.mes-hall↗
arXiv2017

Controlled dynamic screening of excitonic complexes in 2D semiconductors

We report a combined theoretical/experimental study of dynamic screening of excitons in media with frequency-dependent dielectric functions. We develop an analytical model showing that interparticle interactions in an exciton are screened in the range of frequencies from zero to the characteristic binding energy depending on the symmetries and transition energies of that exciton. The problem of the dynamic screening is then reduced to simply solving the Schrodinger equation with an effectively frequency-independent potential. Quantitative predictions of the model are experimentally verified using a test system: neutral, charged and defect-bound excitons in two-dimensional monolayer WS2, screened by metallic, liquid, and semiconducting environments. The screening-induced shifts of the excitonic peaks in photoluminescence spectra are in good agreement with our model.

cond-mat.mes-hall↗
arXiv2016

Renormalization of Optical Transition Strengths in Semiconductor Nanoparticles due to Band Mixing

Unique optical properties of semiconductor nanoparticles (SN) make them very promising in the multitude of applications including lasing, light emission and photovoltaics. In many of these applications it is imperative to understand the physics of interaction of electrons in a SN with external electromagnetic fields on the quantitative level. In particular, the strength of electron-photon coupling determines such important SN parameters as the radiative lifetime and absorption cross section. This strength is often assumed to be fully encoded by the so called Kane momentum matrix element. This parameter, however, pertains to a bulk semiconductor material and, as such, is not sensitive to the quantum confinement effects in SNs. In this work we demonstrate that the quantum confinement, via the so called band mixing, can result in a significant suppression of the strength of electron interaction with electromagnetic field. Within the envelope function formalism we show how this suppression can be described by introducing an effective energy-dependent Kane momentum. Then, the effect of band mixing on the efficiencies of various photoinduced processes can be fully captured by the conventional formulae (e.g., spontaneous emission rate), once the conventional Kane momentum is substituted with the renormalized energy-dependent Kane momentum introduced in here. As an example, we evaluate the energy-dependent Kane momentum for spherical $\rm{PbSe}$ and $\rm{PbS}$ SNs (i.e., quantum dots) and show that neglecting band mixing in these systems can result in the overestimation of absorption cross sections and emission rates by a factor of $\sim$2.

cond-mat.mes-hall↗
arXiv2016

Valence band electronic structure evolution of graphene oxide upon thermal annealing for optoelectronics

We report valence band electronic structure evolution of graphene oxide (GO) upon its thermal reduction. Degree of oxygen functionalization was controlled by annealing temperatures, and an electronic structure evolution was monitored using real-time ultraviolet photoelectron spectroscopy. We observed a drastic increase in density of states around the Fermi level upon thermal annealing at ~600 oC. The result indicates that while there is an apparent band gap for GO prior to a thermal reduction, the gap closes after an annealing around that temperature. This trend of band gap closure was correlated with electrical, chemical, and structural properties to determine a set of GO material properties that is optimal for optoelectronics. The results revealed that annealing at a temperature of ~500 oC leads to the desired properties, demonstrated by a uniform and an order of magnitude enhanced photocurrent map of an individual GO sheet compared to as-synthesized counterpart.

cond-mat.mtrl-sci↗
arXiv2016

Landauer's formula with finite-time relaxation: Kramers' crossover in electronic transport

Landauer's formula is the standard theoretical tool to examine ballistic transport in nano- and meso-scale junctions, but it necessitates that any variation of the junction with time must be slow compared to characteristic times of the system, e.g., the relaxation time of local excitations. Transport through structurally dynamic junctions is, however, increasingly of interest for sensing, harnessing fluctuations, and real-time control. Here, we calculate the steady-state current when relaxation of electrons in the reservoirs is present and demonstrate that it gives rise to three regimes of behavior: weak relaxation gives a contact-limited current; strong relaxation localizes electrons, distorting their natural dynamics and reducing the current; and in an intermediate regime the Landauer view of the system only is recovered. We also demonstrate that a simple equation of motion emerges, which is suitable for efficiently simulating time-dependent transport.

cond-mat.mes-hall↗
arXiv2015

Crossover behavior of the thermal conductance and Kramers' transition rate theory

Kramers' theory frames chemical reaction rates in solution as reactants overcoming a barrier in the presence of friction and noise. For weak coupling to the solution, the reaction rate is limited by the rate at which the solution can restore equilibrium after a subset of reactants have surmounted the barrier to become products. For strong coupling, there are always sufficiently energetic reactants. However, the solution returns many of the intermediate states back to the reactants before the product fully forms. Here, we demonstrate that the thermal conductance displays an analogous physical response to the friction and noise that drive the heat current through a material or structure. A crossover behavior emerges where the thermal reservoirs dominate the conductance at the extremes and only in the intermediate region are the intrinsic properties of the lattice manifest. Not only does this shed new light on Kramers' classic turnover problem, this result is significant for the design of devices for thermal management and other applications, as well as the proper simulation of transport at the nanoscale.

cond-mat.stat-mech↗
arXiv2015

Excitonic effects in two-dimensional semiconductors: Path integral Monte Carlo approach

One of the most striking features of novel 2D semiconductors (e.g., transition metal dichalcogenide monolayers or phosphorene) is a strong Coulomb interaction between charge carriers resulting in large excitonic effects. In particular, this leads to the formation of multi-carrier bound states upon photoexcitation (e.g., excitons, trions and biexcitons), which could remain stable at near-room temperatures and contribute significantly to optical properties of such materials. In the present work we have used the Path Integral Monte Carlo methodology to numerically study properties of multi-carrier bound states in 2D semiconductors. Specifically, we have accurately investigated and tabulated the dependence of single exciton, trion and biexciton binding energies on the strength of dielectric screening, including the limiting cases of very strong and very weak screening. The results of this work are potentially useful in the analysis of experimental data and benchmarking of theoretical and computational models.

cond-mat.mes-hall↗
arXiv2015

Geometric universality of plasmon modes in graphene nanoribbon arrays

Graphene plasmonics is a rapidly growing field with multiple potential applications. One of the standard ways to study plasmons in graphene is by fabricating an array of graphene nanoribbons where nanoribbon edges provide the efficient photon-plasmon coupling. We systematically analyze the problem of optical plasmonic response in such systems and demonstrate the purely geometric nature of the size quantization condition for graphene plasmons. Accurate numerical calculations allowed us to tabulate the universal geometric parameters of plasmon size quantization, which is expected to become useful in analysis of experimental data on plasmonic response of graphene nanoribbons. A simple analytical theory has also been developed which accurately reproduces all the qualitative features of optical plasmonic response of graphene nanoribbons.

cond-mat.mes-hall↗
arXiv2014

Exciton-plasmaritons in graphene-semiconductor structures

We study strong coupling between plasmons in monolayer charge-doped graphene and excitons in a narrow gap semiconductor quantum well separated from graphene by a potential barrier. We show that the Coulomb interaction between excitons and plasmons result in mixed states described by a Hamiltonian similar to that for exciton-polaritons and derive the exciton-plasmon coupling constant that depends on system parameters. We calculate numerically the Rabi splitting of exciton- plasmariton dispersion branches for several semiconductor materials and find that it can reach values of up to 50 - 100 meV.

cond-mat.mes-hall↗
arXiv2014

Electromigration of bivalent functional groups on graphene

Chemical functionalization of graphene holds promise for various applications ranging from nanoelectronics to catalysis, drug delivery, and nano-assembly. In many of these applications it is critical to assess the rates of electromigration - directed motion of adsorbates along the surface of current-carrying graphene due to the electron wind force. In this paper, we develop an accurate analytical theory of electromigration of bivalent functional groups (epoxide, amine) on graphene. Specifically, we carefully analyze various factors contributing to the electron wind force, such as lattice effects and strong scattering beyond Born approximation, and derive a simple analytical expression for this force. Further, we perform accurate electronic structure theory calculations to parameterize the obtained analytical expression. The obtained results can be generalized to different functional groups and adsorbates, e.g., alkali atoms on graphene.

cond-mat.mes-hall↗
arXiv2013

Low-Temperature Hopping Dynamics with Energy Disorder: Renormalization Group Approach

We formulate a real-space renormalization group (RG) approach for efficient numerical analysis of the low-temperature hopping dynamics in energy-disordered lattices. The approach explicitly relies on the time-scale separation of the trapping/escape dynamics. This time-scale separation allows to treat the hopping dynamics as a hierarchal process, an RG step being a transformation between the levels of the hierarchy. We apply the proposed RG approach to analyze hopping dynamics in one- and two-dimensional lattices with varying degree of energy disorder, and find the approach to be more accurate at low temperatures and computationally much faster, than the direct diagonalization. Applicability criteria of the proposed approach with respect to the time-scale separation and the maximum number of hierarchy levels are formulated. RG flows of energy distribution and preexponents of the Miller-Abrahams model are analyzed.

cond-mat.mes-hall↗