Statistical properties of inelastic Lorentz gas

The inelastic Lorentz gas in cooling states is studied. It is found that the inelastic Lorentz gas is localized and that the mean square displacement of the inelastic Lorentz gas obeys a power of a logarithmic function of time. It is also found that the scaled position distribution of the inelastic Lorentz gas has an exponential tail, while the distribution is close to the Gaussian near the peak. Using a random walk model, we derive an analytical expression of the mean square displacement as a function of time and the restitution coefficient, which well agrees with the data of our simulation. The exponential tail of the scaled position distribution function is also obtained by the method of steepest descent.Comment: 31pages,9figures, to appear Journal of Physical Society of Japan Vol.70 No.7 (2001

Photoexcited electron and hole dynamics in semiconductor quantum dots: phonon-induced relaxation, dephasing, multiple exciton generation and recombination.

Photoexcited dynamics of electrons and holes in semiconductor quantum dots (QD), including phonon-induced relaxation, multiple exciton generation, fission and recombination (MEG, MEF and MER), were simulated by combining ab initio time-dependent density functional theory and non-adiabatic molecular dynamics. These nonequilibrium phenomena govern the optical properties and photoexcited dynamics of QDs, determining the branching between electronic processes and thermal energy losses. Our approach accounts for QD size and shape as well as defects, core-shell distribution, surface ligands and charge trapping, which significantly influence the properties of photoexcited QDs. The method creates an explicit time-domain representation of photoinduced processes and describes various kinetic regimes owing to the non-perturbative treatment of quantum dynamics. QDs of different sizes and materials, with and without ligands, are considered. The simulations provide direct evidence that the high-frequency ligand modes on the QD surface play a pivotal role in the electron-phonon relaxation, MEG, MEF and MER. The insights reported here suggest novel routes for controlling the photoinduced processes in semiconductor QDs and lead to new design principles for increasing the efficiencies of photovoltaic devices

Ultrafast exciton transfers in DNA and its nonlinear optical spectroscopy

We have calculated the nonlinear response function of a DNA duplex helix including the contributions from the exciton population and coherence transfers by developing an appropriate exciton theory as well as by utilizing a projector operator technique. As a representative example of DNA double helices, the B-form (dA)10-(dT)10 is considered in detail. The Green functions of the exciton population and coherence transfer processes were obtained by developing the DNA exciton Hamiltonian. This enables us to study the dynamic properties of the solvent relaxation and exciton transfers. The spectral density describing the DNA base-solvent interactions was obtained by adjusting the solvent reorganization energy to reproduce the absorption and steady-state fluorescence spectra. The time-dependent fluorescence shift of the model DNA system is found to be ultrafast and it is largely determined by the exciton population transfer processes. It is further shown that the nonlinear optical spectroscopic techniques such as photon echo peak shift and two-dimensional photon echo can provide important information on the exciton dynamics of the DNA double helix. We have found that the exciton-exciton coherence transfer plays critical roles in the peculiar energy transfer and ultrafast memory loss of the initially created excitonic state in the DNA duplex helix

Distinct structural and dynamical difference between supercooled and normal liquids of hydrogen molecules.

Supercooled hydrogen liquid as well as superfluid have continued to elude experimental observation due to rapid crystallization. We computationally realized and investigated supercooled hydrogen liquid by a recently developed non-empirical real-time molecular dynamics method, which describes non-spherical hydrogen molecules with the nuclear quantum effects. We demonstrated that the hydrogen supercooled liquid is not a simply cooled liquid but rather exhibits intrinsic structural and dynamical characters including a precursor of tunneling and superfluidity which neither normal hydrogen liquid nor solid possesses. All of the insights provide a milestone for planning experiments of metastable hydrogen systems like glassy and superfluid states and for identifying various unknown hydrogen phases

Fast T-Type Photochromism of Colloidal Cu-Doped ZnS Nanocrystals

This paper reports on durable and nearly temperature-independent (at 298–328 K) T-type photochromism of colloidal Cu-doped ZnS nanocrystals (NCs). The color of Cu-doped ZnS NC powder changes from pale yellow to dark gray by UV light irradiation, and the color changes back to pale yellow on a time scale of several tens of seconds to minutes after stopping the light irradiation, while the decoloration reaction is accelerated to submillisecond in solutions. This decoloration reaction is much faster than those of conventional inorganic photochromic materials. The origin of the reversible photoinduced coloration is revealed to be a strong optical transition involving a delocalized surface hole which survives over a minute after escaping from intraparticle carrier recombination due to electron-hopping dissociation. ZnS NCs can be easily prepared in a water-mediated one-pot synthesis and are less toxic. Therefore, they are promising for large-scale photochromic applications such as windows and building materials in addition to conventional photochromic applications. Moreover, the present study demonstrates the importance of excited carrier dynamics and trap depths, resulting in coloration over minutes not only for photochromic nanomaterials but also for various advanced photofunctional materials, such as long persistent luminescent materials and photocatalytic nanomaterials

Molecular Sieving of Propyne/Propylene by a Scalable Nanoporous Crystal with Confined Rotational Shutters

Soft porous coordination polymers (PCPs) have the remarkable ability to recognize similar molecules as a result of their structural dynamics. However, their guest-induced gate-opening behaviors often lead to issues with selectivity and separation efficiency, as co-adsorption is nearly unavoidable. Herein, we report a strategy of a confined-rotational shutter, in which the rotation of pyridyl rings within the confined nanospace of a halogen-bonded coordination framework (NTU-88) creates a maximum aperture of 4.4 Å, which is very close to the molecular size of propyne (C3H4: 4.4 Å), but smaller than that of propylene (C3H6: 5.4 Å). This has been evidenced by crystallographic analyses and modelling calculations. The NTU-88o (open phase of activated NTU-88) demonstrates dedicated C3H4 adsorption, and thereby leads to a sieving separation of C3H4/C3H6 under ambient conditions. The integrated nature of high uptake ratio, considerable capacity, scalable synthesis, and good stability make NTU-88 a promising candidate for the feasible removal of C3H4 from C3H4/C3H6 mixtures. In principle, this strategy holds high potential for extension to soft families, making it a powerful tool for optimizing materials that can tackle challenging separations with no co-adsorption, while retaining the crucial aspect of high capacity.</p

Auger-assisted electron transfer from photoexcited semiconductor quantum dots

Although quantum confined nanomaterials, such as quantum dots (QDs) have emerged as a new class of light harvesting and charge separation materials for solar energy conversion, theoretical models for describing photoinduced charge transfer from these materials remain unclear. In this paper, we show that the rate of photoinduced electron transfer from QDs (CdS, CdSe, and CdTe) to molecular acceptors (anthraquinone, methylviologen, and methylene blue) increases at decreasing QD size (and increasing driving force), showing a lack of Marcus inverted regime behavior over an apparent driving force range of ∼0-1.3 V. We account for this unusual driving force dependence by proposing an Auger-assisted electron transfer model in which the transfer of the electron can be coupled to the excitation of the hole, circumventing the unfavorable Franck-Condon overlap in the Marcus inverted regime. This model is supported by computational studies of electron transfer and trapping processes in model QD-acceptor complexes

Detailed balance has a counterpart in non-equilibrium steady states

When modelling driven steady states of matter, it is common practice either to choose transition rates arbitrarily, or to assume that the principle of detailed balance remains valid away from equilibrium. Neither of those practices is theoretically well founded. Hypothesising ergodicity constrains the transition rates in driven steady states to respect relations analogous to, but different from the equilibrium principle of detailed balance. The constraints arise from demanding that the design of any model system contains no information extraneous to the microscopic laws of motion and the macroscopic observables. This prevents over-description of the non-equilibrium reservoir, and implies that not all stochastic equations of motion are equally valid. The resulting recipe for transition rates has many features in common with equilibrium statistical mechanics.Comment: Replaced with minor revisions to introduction and conclusions. Accepted for publication in Journal of Physics

Extended hydrodynamics from Enskog's equation for a two-dimensional system general formalism

Balance equations are derived from Enskog's kinetic equation for a two-dimensional system of hard disks using Grad's moment expansion method. This set of equations constitute an extended hydrodynamics for moderately dense bi-dimensional fluids. The set of independent hydrodynamic fields in the present formulations are: density, velocity, temperature {\em and also}--following Grad's original idea--the symmetric and traceless pressure tensor $p_{ij}$ and the heat flux vector $\mathbf q^{k}$. An approximation scheme similar in spirit to one made by Grad in his original work is made. Once the hydrodynamics is derived it is used to discuss the nature of a simple one-dimensional heat conduction problem. It is shown that, not too far from equilibrium, the nonequilibrium pressure in this case only depends on the density, temperature and heat flux vector.Comment: :9 pages, 1 figure, This will appear in J. Stat. Phys. with minor corrections and corresponds to Ref[9] of cond-mat/050710