arXiv subjects

Oleg V. Prezhdo

Publications and source records attributed to Oleg V. Prezhdo.

27 records · Page 2Linked to original sources

arXiv2012

A New Model of Chemical Bonding in Ionic Melts

We developed a new physical model to predict macroscopic properties of inorganic molten systems using a realistic description of inter-atomic interactions. Unlike the conventional approach, which tends to overestimate viscosity by several times, our systems consist of a set of ions with an admixture of neutral atoms. The neutral atom subsystem is a consequence of the covalent/ionic state reduction, occurring in the liquid phase. Comparison of the calculated macroscopic properties (shear viscosity and self-diffusion constants) with the experiment demonstrates good performance of our model. The presented approach is inspired by a significant degree of covalent interaction between the alkali and chlorine atoms, predicted by the coupled cluster theory.

cond-mat.mtrl-sci↗

arXiv2012

Acetonitrile Drastically Boosts Conductivity of Ionic Liquids

We apply a new methodology in the force field generation (PCCP 2011, 13, 7910) to study the binary mixtures of five imidazolium-based room-temperature ionic liquids (RTILs) with acetonitrile (ACN). The investigated RTILs are composed of tetrafluoroborate (BF4) anion and dialkylimidazolium cations, where one of the alkyl groups is methyl for all RTILs, and the other group is different for each RTILs, being ethyl (EMIM), butyl (BMIM), hexyl (HMIM), octyl (OMIM), and decyl (DMIM). Specific densities, radial distribution functions, ionic cluster distributions, heats of vaporization, diffusion constants, shear viscosities, ionic conductivities, and their correlations are discussed. Upon addition of ACN, the ionic conductivity of RTILs is found to increase by more than 50 times, that significantly exceeds an impact of most known solvents. Remarkably, the sharpest conductivity growth is found for the long-tailed imidazolium-based cations. This new fact motivates to revisit an application of these binary systems as advanced electrolytes. The ionic conductivity correlates generally with a composition of ionic clusters, simplifying its predictability. In turn, the addition of ACN exponentially increases diffusion and decreases viscosity of the imidazolium-based RTILs/ACN mixtures. Large amounts of acetonitrile stabilize ion pairs, but ruin greater ionic clusters.

cond-mat.mtrl-sci↗

arXiv2012

Confinement by Carbon Nanotubes Drastically Alters the Boiling and Critical Behavior of Water Droplets

Vapor pressure grows rapidly above the boiling temperature, and past the critical point liquid droplets disintegrate. Our atomistic simulations show that this sequence of events is reversed inside carbon nanotubes (CNT). Droplets disintegrate first and at low temperature, while pressure remains small. The droplet disintegration temperature is independent of the CNT diameter. In contrast, depending on CNT diameter, a temperature that is much higher than the bulk boiling temperature is required to raise the internal pressure. The control over pressure by CNT size can be useful for therapeutic drug delivery.

cond-mat.mtrl-sci↗

arXiv2011

Mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and acetonitrile: a molecular simulation

Recently, we introduced a new force field (FF) to simulate transport properties of imidazolium-based room-temperature ionic liquids (RTILs) using a solid physical background. In the present work, we apply this FF to derive thermodynamic, structure, and transport properties of the mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4], and acetonitrile (ACN) over the whole composition range. Three approaches to derive a force field are formulated based on different treatments of the ion-ion and ion-molecule Coulomb interactions using unit-charge, scaled-charge and floating-charge approaches. The simulation results are justified with the help of experimental data on specific density and shear viscosity for these mixtures. We find that a phenomenological account (particularly, simple scaled-charge model) of electronic polarization leads to the best-performing model. Remarkably, its validity does not depend on the molar fraction of [BMIM][BF4] in the mixture. The derived FF is so far the first molecular model which is able to simulate all transport properties of the mixtures, comprising RTIL and ACN, fully realistically.

cond-mat.mtrl-sci↗

arXiv2004

Electronic energy transfer: vibrational control and nonlinear wavepacket interferometry

The time-development of photoexcitations in molecular aggregates exhibits specific dynamics of electronic states and vibrational wavefunction. We discuss the dynamical formation of entanglement between electronic and vibrational degrees of freedom in molecular aggregates with theory of electronic energy transfer and the method of vibronic 2D wavepackets [Cina, Kilin, Humble, J. Chem. Phys. 118, 46 (2003)]. The vibronic dynamics is also described by applying Jaynes-Cummings model to the electronic energy transfer [Kilin, Pereverzev, Prezhdo, J. Chem. Phys. 120, 11209 (2004);math-ph/0403023]. Following the ultrafast excitation of donor[chem-ph/9411004] the population of acceptor rises by small portions per each vibrational period, oscillates force and back between donor and acceptor with later damping and partial revivals of this oscillation. The transfer rate gets larger as donor wavepacket approaches the acceptor equilibrium configuration, which is possible at specific energy differences of donor and acceptor and at maximal amount of the vibrational motion along the line that links donor and acceptor equilibria positions. The four-pulse phase-locked nonlinear wavepacket 2D interferograms reflect the shape of the relevant 2D vibronic wavepackets and have maxima at longer delay between excitation pulses for dimers with equal donor-acceptor energy difference compare to dimers with activationless energy configuration [Cina, Fleming, J. Phys. Chem. A. 108, 11196 (2004)].

quant-ph↗

arXiv2004

Electron-nuclear correlations for photo-induced dynamics in molecular dimers

Ultrafast photoinduced dynamics of electronic excitation in molecular dimers is drastically affected by the dynamic reorganization of inter- and intra- molecular nuclear configuration modeled by a quantized nuclear degree of freedom [Cina et. al, J. Chem Phys. {118}, 46 (2003)]. The dynamics of the electronic population and nuclear coherence is analyzed by solving the chain of coupled differential equations for %mean coordinate, population inversion, electron-vibrational correlation, etc. [Prezhdo, Pereverzev, J. Chem. Phys. {113} 6557 (2000)]. Intriguing results are obtained in the approximation of a small change of the nuclear equilibrium upon photoexcitation. In the limiting case of resonance between the electronic energy gap and the frequency of the nuclear mode these results are justified by comparison to the exactly solvable Jaynes-Cummings model. It is found that the photoinduced processes in the model dimer are arranged according to their time scales: (i) fast scale of nuclear motion, (ii) intermediate scale of dynamical redistribution of electronic population between excited states as well as growth and dynamics of electron-nuclear correlation, (iii) slow scale of electronic population approach to the quasi-equilibrium distribution, decay of electron-nuclear correlation, and decrease of the amplitude of mean coordinate oscillation. The latter processes are accompanied by a noticeable growth of the nuclear coordinate dispersion associated with the overall nuclear wavepacket width. The demonstrated quantum relaxation features of the photoinduced vibronic dynamics in molecular dimers are obtained by a simple method, applicable to systems with many degrees of freedom.

math-ph↗

arXiv1998

Relationship between quantum decoherence times and solvation dynamics in condensed phase chemical systems

A relationship between the time scales of quantum coherence loss and short-time solvent response for a solute/bath system is derived for a Gaussian wave packet approximation for the bath. Decoherence and solvent response times are shown to be directly proportional to each other, with the proportionality coefficient given by the ratio of the thermal energy fluctuations to the fluctuations in the system-bath coupling. The relationship allows the prediction of decoherence times for condensed phase chemical systems from well developed experimental methods.

quant-ph↗

arXiv1996

Mixing Quantum and Classical Mechanics

Using a group theoretical approach we derive an equation of motion for a mixed quantum-classical system. The quantum-classical bracket entering the equation preserves the Lie algebra structure of quantum and classical mechanics: The bracket is antisymmetric and satisfies the Jacobi identity, and, therefore, leads to a natural description of interaction between quantum and classical degrees of freedom. We apply the formalism to coupled quantum and classical oscillators and show how various approximations, such as the mean-field and the multiconfiguration mean-field approaches, can be obtained from the quantum-classical equation of motion.

quant-ph↗

arXiv1996

Solvent mode participation in the non-radiative relaxation of the hydrated electron

Non-adiabatic molecular dynamics simulations are used to analyze the role of different solvent degrees of freedom in the non-radiative relaxation of the first excited state of the hydrated electron. The relaxation occurs through a multi-mode coupling between the adiabatic electronic states. The process cannot be described by a single mode promotion model frequently used in the ``large molecule'' limit of gas phase theories. Solvent librations and vibrations, and the H2O asymmetric stretch in particular, are found to be the most effective promotors of the electronic transition. Dissipation of the released energy to the solvent proceeds on two time scales: a fast 10-20 fs heating of the first solvation shell, where most of the energy is accepted by the librational degrees of freedom, and a several hundred femtosecond global reconstruction of t he solvent as the first shell transfers its excess energy to the rest of the molecules. The implications of our use of a semiclassical approximation as the criterion for good promoting and accepting modes are discussed.

chem-ph↗