Circular polarization of excitonic luminescence in CdTe quantum wells with excess electrons of different densities

The circular polarization of excitonic luminescence is studied in CdTe/Cd1-xMgxTe quantum wells with excess electrons of low density in an external magnetic field. It is observed that the circular polarization of X and X- emissions has opposite signs and is influenced by the excess electron density. If the electron density is relatively high so that the emission intensity of the negatively charged excitons X- is much stronger than that of the neutral excitons X, a stronger circular polarization degree of both X and X- emissions is observed. We find that the circular polarization of both X- and X emissions is caused by the spin polarization of the excess electrons due to the electron-spin-dependent nature of the formation of X-. If the electron density is relatively low and the emission intensity of X- is comparable to that of X, the circular polarization degree of X and X- emissions is considerably smaller. This fact is interpreted as due to a depolarization of the excess electron spins, which is induced by the spin relaxation of X-.

Dry Excess Electrons in Room-Temperature Ionic Liquids

In this article, we describe general trends to be expected at short times when an excess electron is generated or injected in different room-temperature ionic liquids (RTILs). Perhaps surprisingly, the excess electron does not localize systematically on the positively charged cations. Rather, the excess charge localization pattern is determined by the cation and anion HOMO/LUMO gaps and, more importantly, by their relative LUMO alignments. As revealed by experiments, the short-time (ps/ns) transient UV spectrum of excess electrons in RTILs is often characterized by two bands, a broad band at low energies (above 1000 nm) and another weaker band at higher energies (around 400 nm). Our calculations show that the dry or presolvated electron spectrum (fs) also has two similar features. The broad band at low energies is due to transitions between electronic states with similar character on ions of the same class but in different locations of the liquid. The lower-intensity band at higher energies is due to transitions in which the electron is promoted to electronic states of different character, in some cases on counterions. Depending on the chemical nature of the RTIL, and especially on the anions, excess electrons can localize on cations or anions. Our findings hint at possible design strategies for controlling electron localization, where electron transfer or transport across species can be facilitated or blocked depending on the alignment of the electronic levels of the individual species.

Multiple configurations of the two excess 4f electrons on defective CeO2(111):Origin and implications

Density-functional theory calculations have been carried out to systematically study single surface oxygen vacancies on CeO2(111). It is surprisingly found that multiple structures with the two excess electrons localized at different positions can exist. We show that the origin of the multiconfigurations of 4f electrons is a result of geometric relaxation on the surface and strong localization characteristic of 4f electrons in ceria. The importance of 4f electron structures is also presented and discussed. These results may possess implications for our understanding of materials with f electrons.

Excess electron interactions with solvated DNA nucleotides:Strand breaks possible at room temperature

When biological matter is subjected to ionizing radiation, a wealth of secondary low-energy (<20 eV) electrons are produced. These electrons propagate inelastically, losing energy to the medium until they reach energies low enough to localize in regions of high electron affinity. We have recently shown that in fully solvated DNA fragments, nucleobases are particularly attractive for such excess electrons. The next question is what is their longer-term effect on DNA. It has been advocated that they can lead to strand breaks by cleavage of the phosphodiester C-3'-O-3' bond. Here we present a first-principles study of free energy barriers for the cleavage of this bond in fully solvated nucleotides. We have found that except for dAMP, the barriers are on the order of 6 kcal/mol, suggesting that bond cleavage is a regular feature at 300 K. Such low barriers are possible only as a result of solvent and thermal fluctuations. These findings support the notion that low-energy electrons can indeed lead to strand breaks in DNA.

Dynamics of excess electronic charge in aliphatic ionic liquids containing the bis(trifluoromethylsulfonyl)amide anion

In a recent article (J. Am. Chem. Soc. 2011, 133, 20186) we investigated the initial spatial distribution of dry excess electrons in a series of room-temperature ionic liquids (RTILs). Perhaps unexpectedly, we found that in some alkylammonium-based systems the excess negative charge resided on anions and not on the positive cations. Following on these results, in the current paper we describe the time evolution of an excess electronic charge introduced in alkylammonium- and pyrrolidinium-based ionic liquids coupled with the bis(trifluoromethylsulfonyl)amide ([TfN]) anion. We find that on a 50 fs time scale an initially delocalized excess electron localizes on a single [TfN] anion which begins a fragmentation process. Low-energy transitions have a very different physical origin on the several femtoseconds time scale when compared to what occurs on the picosecond time scale. At time zero, these are intraband transitions of the excess electron. However after 40 fs when the excess electronic charge localizes on a single anion, these transitions disappear, and the spectrum is dominated by electron-transfer transitions between the fragments of the doubly charged breaking anion. © 2013 American Chemical Society.

Protection of DNA against low-energy electrons by amino acids: A first-principles molecular dynamics study

Using first-principles molecular dynamics simulations, we have investigated the notion that amino acids can play a protective role when DNA is exposed to excess electrons produced by ionizing radiation. In this study we focus on the interaction of glycine with the DNA nucleobase thymine. We studied thymine-glycine dimers and a condensed phase model consisting of one thymine molecule solvated in amorphous glycine. Our results show that the amino acid acts as a protective agent for the nucleobase in two ways. If the excess electron is initially captured by the thymine, then a proton is transferred in a barrier-less way from a neighboring hydrogen-bonded glycine. This stabilizes the excess electron by reducing the net partial charge on the thymine. In the second mechanism the excess electron is captured by a glycine, which acts as a electron scavenger that prevents electron localization in DNA. Both these mechanisms introduce obstacles to further reactions of the excess electron within a DNA strand, e.g. by raising the free energy barrier associated with strand breaks.

Analyzing hysteresis behavior of capacitance-voltage characteristics of IZO/C₆₀/pentacene/Au diodes with a hole-transport electron-blocking polyterpenol layer by electric-field-induced optical second-harmonic generation measurement

By using electric-field-induced optical second-harmonic generation (EFISHG) measurement, we analyzed hysteresis behavior of capacitance-voltage (C-V) characteristics of IZO/polyterpenol (PT)/C₆₀/pentacene/Au diodes, where PT layer is actively working as a hole-transport electron-blocking layer. The EFISHG measurement verified the presence of interface accumulated charges in the diodes, and showed that a space charge electric field from accumulated excess electrons (holes) that remain at the PT/C₆₀ (C₆₀/pentacene) interface is responsible for the hysteresis loop observed in the C-V characteristics.

Experimental measurement of microwave-induced electron spin-flip time

The electron spin resonance (ESR) is optically detected by monitoring the microwave-induced changes in the circular polarization of the neutral exciton (X) and the negatively charged exciton (X-) emission in CdTe quantum wells with low density of excess electrons. We find that the circular polarization of the X and X- emission is a mapping of the spin polarization of excess electrons. By analyzing the ESR-induced decrease in the circular polarization degree of the X emission, we deduce the microwave-induced electron spin-flip time >0.1 mus, which is much longer than the recombination time of X and X-. This demonstrates that the optically detected ESR in type I quantum wells with low density of excess electrons does not obey the prerequisite for the conventional optically detected magnetic resonance. (C) 2001 American Institute of Physics.

The interaction between adsorbed OH and O-2 on TiO2 surfaces

Reduced TiO2 (110) surfaces usually have OH groups as a result of H2O dissociation at oxygen vacancy defects. Because of excess electrons due to OH adsorption, OH/TiO2. exhibit interesting properties favorable to further O-2 or H2O adsorption. Both O-2 and H2O can adsorb and easily diffuse on the OH/TiO2 surface; such behavior plays a significant role in photocatalysis, heterogeneous catalysis, electronic devices and sensors. Indeed, the processes of H2O dissociation, O-2 and H2O diffusion on Such TiO2 surfaces, in the presence of OH groups, are important issues in their own right. Herein, the most recent experimental and theoretical progresses in understanding the interactions between adsorbed OH groups and O-2, or H2O, over TiO2 (110) surfaces and their implications will be reviewed. (c) 2009 Elsevier Ltd. All rights reserved.

Electronic charge transfer between ceria surfaces and gold adatoms: a GGA+U investigation

We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate electronic aspects of the interaction between ceria surfaces and gold atoms. Our results show that Au adatoms at the (111) surface of ceria can adopt Au0, Au+ or Au� electronic configurations depending on the adsorption site. The strongest adsorption sites are on top of the surface oxygen and in a bridge position between two surface oxygen atoms, and in both cases charge transfer from the gold atom to one of the Ce cations at the surface is involved. Adsorption at other sites, including the hollow sites of the surface, and an O–Ce bridging site, is weaker and does not involve charge transfer. Adsorption at an oxygen vacancy site is very strong and involves the formation of an Au� anion. We argue that the ability of gold atoms to stabilise oxygen vacancies at the ceria surface by moving into the vacancy site and attracting the excess electrons of the defect could be responsible for the enhanced reducibility of ceria surfaces in the presence of gold. Finally, we rationalise the differences in charge transfer behaviour from site to site in terms of the electrostatic potential at the surface and the coordination of the species.

Arbitrary amplitude ion-acoustic solitary excitations in the presence of excess superthermal electrons

Velocity distribution functions with an excess of superthermal particles are commonly observed in space plasmas, and are effectively modeled by a kappa distribution. They are also found in some laboratory experiments. In this paper we obtain existence conditions for and some characteristics of ion-acoustic solitary waves in a plasma composed of cold ions and kappa-distributed electrons, where kappa>3/2 represents the spectral index. As is the case for the usual Maxwell-Boltzmann electrons, only positive potential solitons are found, and, as expected, in the limit of large kappa one recovers the usual range of possible soliton Mach numbers, viz., 1 < M < 1.58. For lower values of kappa, modeling the presence of a greater superthermal component, the range of accessible Mach numbers is reduced. It is found that the amplitude of the largest possible solitons that may be generated in a given plasma (corresponding to the highest allowed Mach number for the given plasma composition) falls off with decreasing kappa, i.e., an increasing superthermal component. On the other hand, at fixed Mach number, both soliton amplitude and profile steepness increase as kappa is decreased. These changes are seen to be important particularly for kappa < 4, i.e., when the electrons have a "hard" spectrum.

Oblique electrostatic excitations in a magnetized plasma in the presence of excess superthermal electrons

The nonlinear propagation of ion-acoustic waves is considered in a magnetized plasma, composed of kappa distributed electrons and an inertial ion fluid. The fluid-dynamical system of equations governing the dynamics of ion-acoustic waves is reduced to a pseudoenergy-balance equation. The properties of arbitrary amplitude, obliquely propagating ion-acoustic solitary waves are thus investigated via a mechanical-motion analog (Sagdeev potential) approach. The presence of excess superthermal electrons is shown to influence the nature of magnetized ion-acoustic solitons. The influence on the soliton characteristics of relevant physical parameters such as obliqueness (the angle between soliton propagation direction and magnetic field), the electron deviation from a Maxwellian ("superthermality") and the soliton speed is investigated.

Electrostatic solitary waves in the presence of excess superthermal electrons: modulational instability and envelope soliton modes

The nonlinear dynamics of electrostatic solitary waves in the form of localized modulated wavepackets is investigated from first principles. Electron-acoustic (EA) excitations are considered in a two-electron plasma, via a fluid formulation. The plasma, assumed to be collisionless and uniform (unmagnetized), is composed of two types of electrons (inertial cold electrons and inertialess kappa-distributed superthermal electrons) and stationary ions. By making use of a multiscale perturbation technique, a nonlinear Schrodinger equation is derived for the modulated envelope, relying on which the occurrence of modulational instability (MI) is investigated in detail. Stationary profile localized EA excitations may exist, in the form of bright solitons (envelope pulses) or dark envelopes (voids). The presence of superthermal electrons modifies the conditions for MI to occur, as well as the associated threshold and growth rate. The concentration of superthermal electrons (i.e., the deviation from a Maxwellian electron distribution) may control or even suppress MI. Furthermore, superthermality affects the characteristics of solitary envelope structures, both qualitatively (supporting one or the other type, for different.) and quantitatively, changing their characteristics (width, amplitude). The stability of bright and dark-type nonlinear structures is confirmed by numerical simulations.

Electron-acoustic solitons in an electron-beam plasma system with kappa-distributed electrons

Interaction of a stream of high-energy electrons with the background plasma plays an important role in the astrophysical phenomena such as interplanetary and stellar bow shock and Earth's foreshock emission. It is not yet fully understood how electrostatic solitary waves are produced at the bow shock. Interestingly, a population of energetic suprathermal electrons were also found to exist in those environments. Previously, we have studied the properties of negative electrostatic potential solitary structures exist in such a plasma with excess suprathermal electrons. In the present study, we investigate the existence conditions and propagation properties of electron-acoustic solitary waves in a plasma consisting of an electron beam fluid, a cold electron fluid, and hot suprathermal electrons modeled by a kappa-distribution function. The Sagdeev pseudopotential method was used to investigate the occurrence of stationary-profile solitary waves. We have determined how the electron-acoustic soliton characteristics depend on the electron beam parameters. It is found that the existence domain for solitons becomes narrower with an increase in the suprathermality of hot electrons, increasing the beam speed, decreasing the beam-to-cold electron population ratio. These results lead to a better understanding of the formation of electron-acoustic solitary waves observed in those space plasma systems characterized by kappa-distributed electrons and inertial drifting (beam) electrons.