arXiv subjects

Vassiliy Lubchenko

Publications and source records attributed to Vassiliy Lubchenko.

At least 19 recordsLinked to original sources

arXiv2026

The Schrödinger equation in the complex plane and quantum entanglement

We formulate a continuity equation for the Schrödinger equation in the complex space. We define a complex momentum by normalizing the complex current by the particle density. This momentum is a quantum analog of the classical, kinematic momentum analytically continued into the complex plane. The kinematic momentum and the gradient of the wavefunction's phase each represent a fluid-like flow in the complex plane; the phase-gradient flow is incompressible. The zeros of the wavefunction give rise to simple poles in the momentum. The poles manifest as irrotational vortexes in the phase-gradient flow, while critical points of the wavefunction present as rigid body-like rotational flows of the kinematic momentum. A discrete nature of elementary excitations comes about inherently because the quantity of the poles is automatically integer. An exact quantization condition is subsequently formulated, which reduces to the Bohr-Sommerfeld condition in the semiclassical limit. We establish a priori that the Bohr-Sommerfeld condition must be exact for the Harmonic Oscillator. We show that the kinetic energy is a sum of contributions of the average value and fluctuations, respectively, of the kinematic momentum. The zero-point vibrations within bound states are solely due to the fluctuations of the momentum and manifest as rigid-body flows at infinity. The momentum poles -- and hence the wavefunction's zeros -- can be viewed as emergent, consistent with the remarkable property of quantum entanglement exhibited by standing wave solutions of the Schrödinger equation.

quant-ph↗

arXiv2026

The two-level systems in cryogenic solids, or how to avoid stressful memories

Structural glasses prepared by bulk quenching a liquid melt universally exhibit puzzling low-energy excitations commonly known as the ``two-level systems'' (TLSs). Recent studies indicate that ultrastable glassy films made by vapor deposition exhibit substantially fewer TLSs and, at the same time, are more stable enthalpically than conventional glasses made by quenching a melt. A similar phenomenon is observed in very stable glasses of model liquid mixtures prepared using swap Monte Carlo sampling. However, in a separate set of enthalpically stable solids, exemplified by amber matured over geological times, the two-level systems persist. In addressing this seeming conflict, we emphasize that a depletion of the TLSs, if any, means the configurational entropy of the material is lower than that of conventional glasses made by bulk-quenching a melt. Ageing does induce reduction in configurational entropy, but amber, we speculate, achieves enthalpic stabilization through increased bonding, not ageing. We separately comment on the discrepancy among existing predictions for the extent of cooperativity of the two-level systems. Several experiments are suggested to test the present picture.

cond-mat.dis-nn↗

arXiv2025

Poly-liquid behaviors of self-associating fluids and mesoscopic aggregation in liquid solutions

In conflict with standard notions of thermodynamics, mesoscopically-sized inclusions (``clusters'') of a solute-rich liquid have been observed in equilibrated solutions of proteins and other molecules. According to a complexation scenario proposed earlier, a steady-state ensemble of finite-sized droplets of a metastable solute-rich liquid can emerge in a solution, if the solute molecules can form transient complexes with each other and/or solute. Here we solve for the thermodynamics of an explicit model of a self-associating fluid in which particles can form transient dimers. We determine ranges of parameters where two distinct dense liquid phases, dimer-rich and monomer-rich respectively, can co-exist with each other and the solute-poor phase. We find that within a certain range of the dimer's binding strength, thermodynamic conditions for mesoscopic clusters to emerge are indeed satisfied. The location and size, respectively, of the corresponding region on the phase diagram are consistent with observation. We predict that the clusters are comprised of a metastable monomer-rich dense liquid, while the bulk solution itself contains substantial amounts of the dimer and exhibits large, pre-critical density fluctuations. Surprisingly, we find that the dense phase commonly observed during the macroscopic liquid-liquid separation should be dimer-rich, another testable prediction. The present findings provide further evidence for the complexation scenario and suggest new experimental ways to test it.

cond-mat.soft↗

arXiv2025

The mechanism of electrical conduction in glassy semiconductors

We argue that the dominant charge carrier in glassy semiconducting alloys is a compound particle in the form of an electron or hole bound to an intimate pair of topological lattice defects; the particle is similar to the polaron solution of the Su-Schrieffer-Heeger Hamiltonian. The spatial component of the density of states for these special polarons is determined by the length scale of spatial modulation of electronegativity caused by a separate set of standalone topological defects. The latter length scale is fixed by the cooperativity size for structural relaxation; the size is largely independent of temperature in the glass but above melting, it decreases with temperature. Thus we predict that the temperature dependence of the electrical conductivity should exhibit a jump in the slope near the glass transition; the size of the jump is predicted to increase with the fragility of the melt. The predicted values of the jump and of the conductivity itself are consistent with experiment.

cond-mat.mes-hall↗

arXiv2024

Knowledge as a Breaking of Ergodicity

We construct a thermodynamic potential that can guide training of a generative model defined on a set of binary degrees of freedom. We argue that upon reduction in description, so as to make the generative model computationally-manageable, the potential develops multiple minima. This is mirrored by the emergence of multiple minima in the free energy proper of the generative model itself. The variety of training samples that employ N binary degrees of freedom is ordinarily much lower than the size 2^N of the full phase space. The non-represented configurations, we argue, should be thought of as comprising a high-temperature phase separated by an extensive energy gap from the configurations composing the training set. Thus, training amounts to sampling a free energy surface in the form of a library of distinct bound states, each of which breaks ergodicity. The ergodicity breaking prevents escape into the near continuum of states comprising the high-temperature phase; thus it is necessary for proper functionality. It may however have the side effect of limiting access to patterns that were underrepresented in the training set. At the same time, the ergodicity breaking within the library complicates both learning and retrieval. As a remedy, one may concurrently employ multiple generative models -- up to one model per free energy minimum.

cs.AI↗

arXiv2024

Cavitation in Electron Fluids and the Puzzles of Photoemission Spectra in Alkali Metals

Angle-resolved photoemission spectra of alkali metals exhibit a puzzling, non-dispersing peak in the apparent density of states near the Fermi energy. We argue that the holes left behind a significant fraction of photoejected electrons are not wavepacket-like objects used to describe excitations of an equilibrium Fermi liquid but, instead, are relatively localized entities resulting from a photon-induced cavitation in the electron fluid. At the same time, these special localized holes can be thought of as vacancies in a transient Wigner solid. The corresponding contribution to the photoemission current is non-dispersive and is tied to the Fermi level; it exhibits certain similarities to photoemission from localized core orbitals such as the presence of recoil currents. Calculated spectra are consistent with experiment. We briefly discuss the present findings in the context of quantum measurement.

cond-mat.str-el↗

arXiv2023

Emergence of pseudo-time during optimal Monte Carlo sampling and temporal aspects of symmetry breaking and restoration

We argue that one can associate a pseudo-time with sequences of configurations generated in the course of classical Monte Carlo simulations for a single-minimum bound state, if the sampling is optimal. Hereby the sampling rates can be, under special circumstances, calibrated against the relaxation rate and frequency of motion of an actual physical system. The latter possibility is linked to the optimal sampling regime being a universal crossover separating two distinct suboptimal sampling regimes analogous to the physical phenomena of diffusion and effusion, respectively. Bound states break symmetry; one may thus regard the pseudo-time as a quantity emerging together with the bound state. Conversely, when transport among distinct bound states takes place -- thus restoring symmetry -- a pseudo-time can no longer be defined. One can still quantify activation barriers, if the latter barriers are smooth, but the simulation becomes impractically slow and pertains to overdamped transport only. Specially designed Monte Carlo moves that bypass activation barriers -- so as to accelerate sampling of the thermodynamics -- amount to effusive transport and lead to severe under-sampling of transition-state configurations that separate distinct bound states while destroying the said universality. Implications of the present findings for simulations of glassy liquids are discussed.

cond-mat.stat-mech↗

arXiv2018

Low-temperature anomalies in disordered solids: A cold case of contested relics?

Amorphous solids manifest puzzling effects of mysterious degrees of freedom that give rise to a heat capacity and phonon scattering in great excess over what would be expected for a solid that has a unique vibrational ground state. Of particular conceptual importance is the apparent near universality of phonon scattering in amorphous solids made by quenching a liquid. To rationalise this universality, scale-free scenarios have been proposed that either hinge on there being long-range interactions between bare structural degrees of freedom or that invoke long-range criticality stemming from the emergence of marginally stable vibrational modes. In a contrasting, local scenario, the puzzling low-temperature degrees of freedom are, instead, weakly-interacting, strongly anharmonic degrees of freedom each of which involves the motion of a few hundred particles. In this scenario, the universality of phonon scattering comes about because the characteristic energy scale of the local anharmonic resonances and the strength of their interaction with phonons are both set by the glass transition temperature $T_g$, while their concentration is set by the cooperativity size $ξ$ for dynamics at $T_g$. The nanoscopic length $ξ$ is manifested in vibrational excitations of the spatial boundary of the resonances, which underlie the so-called Boson peak, and very deep, topological midgap electronic states in glassy semiconductors, which are implicated in a number of strange optoelectronic phenomena in amorphous chalcogenides. I discuss the merits of the above scenarios when confronted with experimental data.

cond-mat.dis-nn↗

arXiv2018

Temperature-driven narrowing of the insulating gap as a precursor of the insulator-to-metal transition: Implications for the electronic structure of solids

We present a microscopic picture rationalizing the surprisingly steep decrease of the band gap with temperature in insulators, crystalline or otherwise. The gap narrowing largely results from fluctuations of long-wavelength optical phonons---when the latter are present---or their disordered analogs, if the material is amorphous. We elaborate on this notion to show that possibly with the exception of weakly bound solids made of closed-shell atoms, the existence of an insulating gap or pseudo-gap in a periodic solid implies that optical phonons must be present, too. This means that in an insulating solid, the primitive cell must have at least two atoms and/or that a charge density wave is present. As a corollary, a (periodic) elemental solid whose primitive unit contains only one atom will ordinarily be a metal, possibly unless the element belongs to group 18 of the periodic table, consistent with observation. Some implications of the present results for quantum solids are briefly discussed, such as that the ground state of the Wigner crystal must be anti-ferromagnetic. A simple field theory of the metal-insulator transition is constructed that ties long-wavelength optical vibrations with fluctuations of an order parameter for the metal-insulator transition; symmetry-breaking aspects of the latter transition are thereby highlighted.

cond-mat.mtrl-sci↗

arXiv2018

Structural origin of the midgap electronic states and the Urbach tail in pnictogen-chalcogenide glasses

We determine the electronic density of states for computationally-generated bulk samples of amorphous chalcogenide alloys As$_{x}$Se$_{100-x}$. The samples were generated using a structure-building algorithm reported recently by us ({J. Chem. Phys.} ${\bf 147}$, 114505). Several key features of the calculated density of states are in good agreement with experiment: The trend of the mobility gap with arsenic content is reproduced. The sample-to-sample variation in the energies of states near the mobility gap is quantitatively consistent with the width of the Urbach tail in the optical edge observed in experiment. Most importantly, our samples consistently exhibit very deep-lying midgap electronic states that are delocalized significantly more than what would be expected for a deep impurity or defect state; the delocalization is highly anisotropic. These properties are consistent with those of the topological midgap electronic states that have been proposed by Zhugayevych and Lubchenko as an explanation for several puzzling opto-electronic anomalies observed in the chalcogenides, including light-induced midgap absorption and ESR signal, and anomalous photoluminescence. In a complement to the traditional view of the Urbach states as a generic consequence of disorder in atomic positions, the present results suggest these states can be also thought of as intimate pairs of topological midgap states that cannot recombine because of disorder. Finally, samples with an odd number of electrons exhibit neutral, spin $1/2$ midgap states as well as polaron-like configurations that consist of a charge carrier bound to an intimate pair of midgap states; the polaron's identity---electron or hole---depends on the preparation protocol of the sample.

cond-mat.mtrl-sci↗

arXiv2018

A mechanism for reversible mesoscopic aggregation in liquid solutions

We show systematically that a steady-state ensemble of mesoscopic inclusions of a solute-rich fluid can emerge in liquid solutions well outside the region of stability of the solute-rich phase. Unanticipated by conventional treatments, this type of reversible aggregation nonetheless can take place if the solute molecules bind transiently with each other to form long-lived complexes. The binding causes kinetic stabilization of inclusions of the solute-rich phase---within a substantial size range---so as to render the critical size for nucleation of the inclusions finite. Individual droplets nucleate and grow until they become mechanically unstable because of a concomitant drop in the internal pressure, the latter drop caused by the thermodynamic metastability of the solute-rich phase. At the same time, the {\em ensemble} of the droplets is steady-state on long times. In a freshly prepared solution, the ensemble is predicted to evolve similarly to the conventional Ostwald ripening, during which larger droplets grow at the expense of smaller droplets. The present mechanism is proposed to underlie the puzzling mesoscopic clusters observed in solutions of proteins and other molecules.

cond-mat.soft↗

arXiv2017

Aging, jamming, and the limits of stability of amorphous solids

Apart from not having crystallized, supercooled liquids can be considered as being properly equilibrated and thus can be described by a few thermodynamic control variables. In contrast, glasses and other amorphous solids can be arbitrarily far away from equilibrium and require a description of the history of the conditions under which they formed. In this paper we describe how the locality of interactions intrinsic to finite-dimensional systems affects the stability of amorphous solids far off equilibrium. Our analysis encompasses both structural glasses formed by cooling and colloidal assemblies formed by compression. A diagram outlining regions of marginal stability can be adduced which bears some resemblance to the quasi-equilibrium replica meanfield theory phase diagram of hard sphere glasses in high dimensions but is distinct from that construct in that the diagram describes not true phase transitions but kinetic transitions that depend on the preparation protocol. The diagram exhibits two distinct sectors. One sector corresponds to amorphous states with relatively open structures, the other to high density, more closely-packed ones. The former transform rapidly owing to there being motions with no free energy barriers; these motions are string-like locally. In the dense region, amorphous systems age via compact activated reconfigurations. The two regimes correspond, in equilibrium, to the collisional or uniform liquid and the so called landscape regime, respectively. These are separated by a spinodal line of dynamical crossovers. Owing to the rigidity of the surrounding matrix in the landscape, high-density part of the diagram, a sufficiently rapid pressure quench adds compressive energy which also leads to an instability toward string-like motions with near vanishing barriers. (SEE REST OF ABSTRACT IN THE ARTICLE.)

cond-mat.dis-nn↗

arXiv2017

The chemical bond as an emergent phenomenon

We first argue that the covalent bond and the various closed-shell interactions can be thought of as symmetry broken versions of one and the same interaction, viz., the multi-center bond. We use specially chosen molecular units to show that the symmetry breaking is controlled by density and electronegativity variation. We show that the bond order changes with bond deformation but in a step-like fashion, regions of near constancy separated by electronic localization transitions. These will often cause displacive transitions as well so that the bond strength, order, and length are established self-consistently. We further argue on the inherent relation of the covalent, closed-shell, and multi-center interactions with ionic and metallic bonding. All of these interactions can be viewed as distinct sectors on a phase diagram with density and electronegativity variation as control variables; the ionic and covalent/secondary sectors are associated with on-site and bond-order charge density wave respectively, the metallic sectorwith an electronic fluid. While displaying a contiguity at low densities, the metallic and ionic interactions represent distinct phases separated by discontinuous transitions at sufficiently high densities. Multi-center interactions emerge as a hybrid of the metallic and ionic bond that results from spatial coexistence of delocalized and localized electrons. In the present description, the issue of the stability of a compound is that of mutual miscibility of electronic fluids with distinct degrees of electron localization, supra-atomic ordering in complex inorganic compounds comes about naturally. The notions of electronic localization advanced hereby suggest a high throughput, automated procedure for screening candidate compounds and structures with regard to stability, without the need for computationally costly geometric optimization.

cond-mat.str-el↗

arXiv2015

Pressure in the Landau-Ginzburg Functional: Pascal's Law, Nucleation in Fluid Mixtures, a Meanfield Theory of Amphiphilic Action, and Interface Wetting in Glassy Liquids

We set up the problem of finding the transition state for phase nucleation in multi-component fluid mixtures, within the Landau-Ginzburg density functional. We establish an expression for the coordinate-dependent local pressure that applies to mixtures, arbitrary geometries, and certain non-equilibrium configurations. The expression allows one to explicitly evaluate the pressure in spherical geometry, à la van der Waals. Pascal's law is recovered within the Landau-Ginzburg density functional theory, formally analogously to how conservation of energy is recovered in the Lagrangian formulation of mechanics. We establish proper boundary conditions for certain singular functional forms of the bulk free energy density that allow one to obtain droplet solutions with thick walls in essentially closed form. The hydrodynamic modes responsible for mixing near the interface are explicitly identified in the treatment; the composition at the interface is found to depend only weakly on the droplet size. Next we develop a Landau-Ginzburg treatment of the effects of amphiphiles on the surface tension; the amphiphilic action is seen as a violation of Pascal's law. We explicitly obtain the binding potential for the detergent at the interface and the dependence of the down-renormalization of the surface tension on the activity of the detergent. Finally, we argue that the renormalization of the activation barrier for escape from long-lived structures in glassy liquids can be viewed as an action of uniformly seeded, randomly oriented amphiphilic molecules on the interface separating two dissimilar aperiodic structures. This renormalization is also considered as a "wetting" of the interface. The resulting conclusions are consistent with the random first order transition (RFOT) theory.

cond-mat.stat-mech↗

arXiv2015

Theory of the Structural Glass Transition: A Pedagogical Review

The random first-order transition (RFOT) theory of the structural glass transition is reviewed in a pedagogical fashion. The rigidity that emerges in crystals and glassy liquids is of the same fundamental origin. In both cases, it corresponds with a breaking of the translational symmetry; analogies with freezing transitions in spin systems can also be made. The common aspect of these seemingly distinct phenomena is a spontaneous emergence of the molecular field, a venerable and well-understood concept. In crucial distinction from periodic crystallisation, the free energy landscape of a glassy liquid is vastly degenerate, which gives rise to new length and time scales while rendering the emergence of rigidity gradual. We obviate the standard notion that to be mechanically stable a structure must be essentially unique; instead, we show that bulk degeneracy is perfectly allowed but should not exceed a certain value. The present microscopic description thus explains both crystallisation and the emergence of the landscape regime followed by vitrification in a unified, thermodynamics-rooted fashion. The article contains a self-contained exposition of the basics of the classical density functional theory and liquid theory, which are subsequently used to quantitatively estimate, without using adjustable parameters, the key attributes of glassy liquids, viz., the relaxation barriers, glass transition temperature, and cooperativity size. These results are then used to quantitatively discuss many diverse glassy phenomena, including: the intrinsic connection between the excess liquid entropy and relaxation rates, the non-Arrhenius temperature dependence of $α$-relaxation, the dynamic heterogeneity, ... (see Comments for the remainder of Abstract.)

cond-mat.dis-nn↗

arXiv2014

On the Mechanism of Activated Transport in Glassy Liquids

We explore several potential issues that have been raised over the years regarding the "entropic droplet" scenario of activated transport in liquids, due to Wolynes and coworkers, with the aim of clarifying the status of various approximations of the random first order transition theory (RFOT) of the structural glass transition. In doing so, we estimate the mismatch penalty between alternative aperiodic structures, above the glass transition; the penalty is equal to the typical magnitude of free energy fluctuations in the liquid. The resulting expressions for the activation barrier and the cooperativity length contain exclusively bulk, static properties; in their simplest form they contains only the bulk modulus and the configurational entropy per unit volume. The expressions are universal in that they do not depend explicitly on the molecular detail. The predicted values for the barrier and cooperativity length and, in particular, the temperature dependence of the barrier are in satisfactory agreement with observation. We thus confirm that the entropic droplet picture is indeed not only internally-consistent but is also fully constructive, consistent with the apparent success of its many quantitative predictions. A simple view of a glassy liquid as a locally metastable, degenerate pattern of frozen-in stress emerges in the present description. Finally, we derive testable relationships between the bulk modulus and several characteristics of glassy liquids and peculiarities in low-temperature glasses.

cond-mat.dis-nn↗

arXiv2014

Self-consistent elastic continuum theory of degenerate, equilibrium aperiodic solids

We show that the vibrational response of a glassy liquid at finite frequencies can be described by continuum mechanics despite the vast degeneracy of the vibrational ground state; standard continuum elasticity assumes a unique ground state. The effective elastic constants are determined by the bare elastic constants of individual free energy minima of the liquid, the magnitude of built-in stress, and temperature, analogously to how the dielectric response of a polar liquid is determined by the dipole moment of the constituent molecules and temperature. In contrast with the dielectric constant---which is enhanced by adding polar molecules to the system---the elastic constants are down-renormalized by the relaxation of the built-in stress. The renormalization flow of the elastic constants has three fixed points, two of which are trivial and correspond to the uniform liquid state and an infinitely compressible solid respectively. There is also a nontrivial fixed point at the Poisson ratio equal to 1/5, which corresponds to an isospin-like degeneracy between shear and uniform deformation. The present description predicts a discontinuous jump in the (finite frequency) shear modulus at the crossover from collisional to activated transport, consistent with the RFOT theory.

cond-mat.dis-nn↗

arXiv2013

Microscopically based calculations of the free energy barrier and dynamic length scale in supercooled liquids: The comparative role of configurational entropy and elasticity

We compute the temperature-dependent barrier for alpha-relaxations in several liquids, without adjustable parameters, using experimentally determined elastic, structural, and calorimetric data. We employ the random first order transition(RFOT) theory, in which relaxation occurs via activated reconfigurations between distinct, aperiodic minima of the free energy. Two different approximations for the mismatch penalty between the distinct aperiodic states are compared, one due to Xia and Wolynes, which scales universally with temperature as for hard spheres, and one due to Rabochiy and Lubchenko, which employs measured elastic and structural data for individual substances. The agreement between the predictions and experiment is satisfactory, given the uncertainty in the measured experimental inputs. The explicitly computed barriers are used to calculate the glass transition temperature for each substance---a kinetic quantity---from the static input data alone. The temperature dependence of both the elastic and structural constants enters the temperature dependence of the barrier over an extended range to a degree that varies from substance to substance. The lowering of the configurational entropy, however, seems to be the dominant contributor to the barrier increase near the laboratory glass transition, consistent with previous experimental tests of the RFOT theory using the XW approximation. In addition, we compute the temperature dependence of the dynamical correlation length, also without using adjustable parameters. These agree well with experimental estimates obtained using the Berthier et al. procedure. Finally, we find the temperature dependence of the complexity of a rearranging region is consistent with the picture based on the RFOT theory but is in conflict with the assumptions of the Adam-Gibbs and "shoving" scenarios for the viscous slowing down in supercooled liquids.

cond-mat.dis-nn↗