Single-electron Excitation Research Articles

Domination of dissociative double-electron excitation over dissociative single-electron excitation in electron collisions with NH3

Domination of dissociative double-electron excitation over dissociative single-electron excitation in electron collisions with <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mi>NH</mml:mi><mml:mn>3</mml:mn></mml:msub></mml:math>

Understanding band gaps of solids in generalized Kohn–Sham theory

The fundamental energy gap of a periodic solid distinguishes insulators from metals and characterizes low-energy single-electron excitations. However, the gap in the band structure of the exact multiplicative Kohn-Sham (KS) potential substantially underestimates the fundamental gap, a major limitation of KS density-functional theory. Here, we give a simple proof of a theorem: In generalized KS theory (GKS), the band gap of an extended system equals the fundamental gap for the approximate functional if the GKS potential operator is continuous and the density change is delocalized when an electron or hole is added. Our theorem explains how GKS band gaps from metageneralized gradient approximations (meta-GGAs) and hybrid functionals can be more realistic than those from GGAs or even from the exact KS potential. The theorem also follows from earlier work. The band edges in the GKS one-electron spectrum are also related to measurable energies. A linear chain of hydrogen molecules, solid aluminum arsenide, and solid argon provide numerical illustrations.

Decoherence and relaxation of a single electron in a one-dimensional conductor

We study the decoherence and relaxation of a single elementary electronic excitation propagating in a one-dimensional chiral conductor. Using two-particle interferences in the electronic analog of the Hong-Ou-Mandel experiment, we analyze quantitatively the decoherence scenario of a single electron propagating along a quantum Hall edge channel at filling factor 2. The decoherence results from the emergence of collective neutral excitations induced by Coulomb interaction and leading, in one dimension, to the destruction of the elementary quasiparticle. This study establishes the relevance of electron quantum optics setups to provide stringent tests of strong interaction effects in one-dimensional conductors described by Luttinger liquids paradigm.

Many-body delocalization transition and relaxation in a quantum dot

We revisit the problem of quantum localization of many-body states in a quantum dot and the associated problem of relaxation of an excited state in a finite correlated electron system. We determine the localization threshold for the eigenstates in Fock space. We argue that the localization-delocalization transition (which manifests itself, e.g., in the statistics of many-body energy levels) becomes sharp in the limit of a large dimensionless conductance (or, equivalently, in the limit of weak interaction). We also analyze the temporal relaxation of quantum states of various types (a "hot-electron state", a "typical" many-body state, and a single-electron excitation added to a "thermal state") with energies below, at, and above the transition.

Electron and electron-hole quasiparticle states in a driven quantum contact

We study the many-body electronic state created by a time-dependent drive of a mesoscopic contact. The many-body state is expressed manifestly in terms of single-electron and electron-hole quasiparticle excitations with the amplitudes and probabilities of creation which depend on the details of the applied voltage. We experimentally probe the time dependence of the constituent electronic states by using an analog of the optical Hong-Ou-Mandel correlation experiment where electrons emitted from the terminals with a relative time delay collide at the contact. The electron wave packet overlap is directly related to the current noise power in the contact. We have confirmed the time dependence of the electronic states predicted theoretically by measurements of the current noise power in a tunnel junction under harmonic excitation.

Unique Electronic Response of a Nanoscale Al/Alumina System

Research is conducted to understand relatively unknown electronic behavior of a nanoscale Al/alumina system. This is acquired by a two-step process where characterization by electron microscopy is first performed for crystallography, followed by electron energy loss spectroscopy for electronic response from spatially inequivalent spots of Al nanoparticles with a protective surface oxide. A novel and unique plasmon from the surface oxide is found in the energy loss spectra between 5 and 6 eV other than the previously reported transitions for individual Al and Al2O3. In the current study, various properties of the new transition are sought by evaluating its dependence on crystal structure and particle size along with related physical functions. The results indicate that the novel transition has collective properties, preceded by a single-electron excitation at a slightly lower energy. Application of the Bethe f-sum rule shows that the concentration of charge carriers reaches around the Mott density by the t...

New constraints for low-momentum electronic excitations in condensed matter: fundamental consequences from classical and quantum dielectric theory

We present new constraints for the transportation behaviour of low-momentum electronic excitations in condensed matter systems, and demonstrate that these have both a fundamental physical interpretation and a significant impact on the description of low-energy inelastic electron scattering. The dispersion behaviour and characteristic lifetime properties of plasmon and single-electron excitations are investigated using popular classical, semi-classical and quantum dielectric models. We find that, irrespective of constrained agreement to the well known high-momentum and high-energy Bethe ridge limit, standard descriptions of low-momentum electron excitations are inconsistent and unphysical. These observations have direct impact on calculations of transport properties such as inelastic mean free paths, stopping powers and escape depths of charged particles in condensed matter systems.

Calculation of energy levels, lifetimes and radiative data for La XXIX to Sm XXXIV

We present the most comprehensive atomic data for La XXIX to Sm XXXIV with single electron excitation from M-shell to N-shell and N-shell to higher shells. We have presented energy levels, lifetimes and radiative data using Multi-configuration Dirac–Fock (MCDF) method for the lowest 27 states belonging to the configuration 3d104l (l=0,1,2,3), 3d105l (l=0,1,2,3,4), 3d106l (l=0,1,2,3,4) and 3d94s2. We have also considered relativistic effects by incorporating quantum electrodynamics (QED) and Breit corrections. We have made comparisons of our presented results with available theoretical as well as experimental results and a good agreement is achieved. Further, we have also reported energy levels by performing distorted wave calculations with fully relativistic flexible atomic code (FAC). The calculations match well with MCDF results. Additionally, we have investigated the effect of nuclear charge on transition wavelength and radiative rates for strong Extreme Ultraviolet (EUV) transitions from n=4→4. We believe that our reported data in this work may be useful in various applications of lanthanide ions related to broad area of research such as applied physics, laser physics and astrophysics etc.

Nonlinear Optical Properties of X(C6H5)4 (X = B(-), C, N(+), P(+)): A New Class of Molecules with a Negative Third-Order Polarizability.

Organic π-conjugated materials have been widely used for a variety of nonlinear optical (NLO) applications. Molecules with negative real components Re(γ) of the third-order polarizability, which leads to nonlinear refraction in macroscopic systems, have important benefits for several NLO applications. However, few organic systems studied to date have negative Re(γ) in the long wavelength limit, and all inorganic materials show positive nonlinear refraction in this limit. Here, we introduce a new class of molecules of the form X(C6H5)4, where X = B(-), C, N(+), and P(+), that have negative Re(γ). The molecular mechanism for the NLO properties in these systems is very different from those in typical linear conjugated systems: These systems have a band of excited states involving single-electron excitations within the π-system, several of which have significant coupling to the ground state. Thus, Re(γ) cannot be understood in terms of a simplified essential-state model and must be analyzed in the context of the full sum-over-states expression. Although Re(γ) is significantly smaller than that of other commonly studied NLO chromophores, the introduction of a new molecular architecture offering the potential for a negative Re(γ) introduces new avenues of molecular design for NLO applications.

First-order correlation function of a stream of single-electron wave packets

The first-order correlation function, which is accessible experimentally, contains all essential information about the state of the system of non-interacting electrons. Here I discuss how this function can be used to answer the question whether the state of a periodic stream of single-electron wave-packets is a multi-particle state or it is the product of single-particle states. In the latter case the correlation function is expected to be factorizable while in the former case it is not. As an example I consider a train of Lorentzian in shape single-electron excitations, levitons. I demonstrate that the correlation function in time domain is factorizable or not depending on whether the wave-packets are separated or overlapping. In contrast, the correlation function in energy domain is always factorizable and thus cannot be used to distinguish single- and multi-particle states.

A Theoretical Study of the Kinetics of the Hydrogen Atom Abstraction Reactions from Cyclopropane by H, O (3P), and Cl (2P3/2) Atoms and OH Radicals

ABSTRACTThe rate constants of the H‐abstraction reactions from cyclopropane by H, O (3P), Cl (2P3/2), and OH radicals have been calculated over the temperature range of 250−2500 K using two different levels of theory. Calculations of optimized geometrical parameters and vibrational frequencies are performed using the MP2 method combined with the cc‐pVTZ basis set and the 6–311++G(d,p) basis set. Single‐point energy calculations have been carried out with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (perturbatively) electron excitations CCSD(T) using either the cc‐pVTZ, aug‐cc‐pVTZ, and aug‐cc‐pVQZ basis sets or the 6–311++G(3df,3pd) basis set. The CCSD(T) calculated potential energies have been extrapolated to the complete basis limit (CBS) limit. The Full Configuration Interaction (FCI) energies have been also estimated using the continued‐fraction approximation as proposed by Goodson (J. Chem. Phys., 2002, 116, 6948–6956). Canonical transition‐state theory combined with an Eckart tunneling correction has been used to predict the rate constants as a function of temperature using two kinetic models (direct abstraction or complex mechanism) at two levels of theory (CCSD(T)‐cf/CBS//MP2/cc‐pVTZ and CCSD(T)‐cf/6–311++G(3df,3pd)//MP2/6–311++G(d,p)). The calculated kinetic parameters are in reasonable agreement with their literature counterparts for all reactions. In the light of these trends, the use of the Pople‐style basis sets for studying the reactivity of other systems such as larger cycloalkanes or halogenated cycloalkanes is recommended because the 6–311++G(3df,3pd) basis set is less time consuming than the aug‐cc‐pVQZ basis set. Based on our calculations performed at the CCSD(T)‐cf/CBS//MP2/cc‐pVTZ level of theory, the standard enthalpy of formation at 298 K for the cyclopropyl radical has been reassessed and its value is (290.5 ± 1.6) kJ mol−1.

Electron impact induced collective and atomic-like single-electron Ga3d → εl excitations in GaAsN alloy

Nitride nanolayer of about 4nm thickness formed on the GaAs (100) surface by N2+ ion bombardment with energy Ei=2500eV has been studied in situ by electron energy loss spectroscopy (EELS). Collective (plasmonic) and single-electron excitations were resolved in the EELS spectrum. Analysis of the plasmonic contributions from different chemical phases showed domination of the phase of GaAsN alloy in the nitrated layer. Single-electron excitations were shown to be related to the transitions from core- and valence band states into unoccupied local atomic-like states Ga3d→εl and “GaAs4p”→εl. The model of the atomic-like state formation in a temporary quantum dot near Ga atom was assumed. It has been shown that analysis of collective and single-electron excitations enables synchronous EELS diagnostics of both the chemical composition and unoccupied states of GaAs nitrides.

Momentum-dependent lifetime broadening of electron energy loss spectra: Sum rule constraints and an asymmetric rectangle toy model

Electron energy loss spectra enable a detailed quantification of the electronic loss mechanisms in a target solid, particularly in the low-energy region dominated by plasmon excitations. Models of the electronic response in condensed-matter systems are usually derived from free-electron gas or jellium models, which commonly neglect to account for the lifetime broadening of individual plasmon and single-electron excitations in a constrained, physical manner. This can lead to potentially significant errors in electron energy loss spectra and electron inelastic mean-free-path (IMFP) calculations. We develop a toy model of plasmon and single-electron excitations that incorporates lifetime broadening for each excitation in an energy- and momentum-dependent fashion. The model is physically constrained using optical and electronic sum rules. We demonstrate the necessity of asymmetric excitation broadening, and show that causally permitted variations in the broadening function can have a significant impact on the dielectric response of the material. Our developments are applied to molybdenum, and compared with previous modeling and high-precision experimental results for the IMFP at electron energies below 120 eV.

Real-time decoherence of Landau and Levitov quasiparticles in quantum Hall edge channels.

Quantum Hall edge channels at integer filling factor provide a unique test bench to understand the decoherence and relaxation of single-electron excitations in a ballistic quantum conductor. In this Letter, we obtain a full visualization of the decoherence scenario of energy (Landau)- and time (Levitov)-resolved single-electron excitations at filling factor ν = 2. We show that the Landau excitation exhibits a fast relaxation followed by spin-charge separation whereas the Levitov excitation only experiences spin-charge separation. We finally suggest to use Hong-Ou-Mandel-type experiments to probe specific signatures of these different scenarios.

Plasmonlike resonances in atomic chains: A time-dependent density-functional theory study

We studied plasmonlike resonances in one-dimensional (1D) atomic chain systems by using time-dependent density-functional theory (TDDFT) and local density functional theory. Recent TDDFT studies have shown the coexistence of longitudinal and transverses collective plasmonlike resonances in the atomic chains of simple and noble metals. Such atomic chains contain only a few atoms. The induced polarization occurs along the atomic chain in longitudinal mode and perpendicular to the atomic chain in transverse mode. To understand the emergence of plasmonlike resonance in 1D atomic chains better, we studied carbon chains in which plasmonic resonances are not expected to occur. We used TDDFT to study the emergence of collective resonances in various forms of carbon chains, cumulenes ${\mathrm{C}}_{n}{\mathrm{H}}_{4}$, polyynes ${\mathrm{C}}_{n}{\mathrm{H}}_{2}$, and alkenes ${\mathrm{C}}_{n}{\mathrm{H}}_{n+2}$. The excitation energy and dipole oscillation strengths of these systems were determined through TDDFT by using the turbomole package. We determined how collective plasmonlike resonances arise from single-electron excitations when the number of electrons increases as the carbon chain lengthens. The collective excitation behavior is then compared with that of metallic atomic chains. Our TDDFT results showed longitudinal collective modes for cumulenes and polyynes, as well as for finite-length chains. These collective excitations exhibit the same behavior as that of longitudinal ``plasmon'' previously identified in sodium and silver chains, although polyynes are gapped in the long chain limit. Such longitudinal excitations are absent in alkenes. However, unlike metal atomic chains, carbon chains exhibited no transverse collective mode. The band structure of periodic atomic chains was calculated by using the standard local density functional method. These structures were used to interpret the results and to relate the single-electron excitation to the collective plasmonlike response. Within the one-particle quantum-well picture, the longitudinal mode in the linear atomic chain arises from intraband transition with $\ensuremath{\Delta}q=1$, where $q$ is the quantum number of quantum wells. $\ensuremath{\Delta}q=1$ intraband transitions can be found in metallic (e.g., Na) chains and in carbon chains (cumulenes and polyynes), such longitudinal collective mode is rather ``generic''. Meanwhile, the transverse modes of the sodium chains are attributed to interband transitions with an even $\ensuremath{\Delta}q$ (dominated by $\ensuremath{\Delta}q=0$), and such transverse collective excitations only form if the allowed $\ensuremath{\Delta}q=0$ transitions occur between bands that are parallel to each other. Such bands can be found in simple metals, but not in carbon chains.

Experimental and DFT/Time‐Dependent DFT Studies on Neutral and One‐Electron‐Reduced Quinoxaline and Pyrazine Precursors and Their Mononuclear (Pd II , Pt II ) Derivatives

Electrochemical and UV/Vis spectral studies on the quinoxaline compound 2,3-di(2-pyridyl)-6,7-dicyano-1,4-quinoxaline, [(CN)2Py2Qx], its metallated derivatives [(CN)2Py2QxMCl2] (M = PdII, PtII) and their analogues sharing the dicyanopyrazine fragment are presented and discussed. X-ray work on the new quinoxaline complex [(CN)2Py2QxPtCl2] establishes that PtII is coordinated to the pyridine N atoms (“py–py” coordination). The spectra of the 1– charged quinoxaline and pyrazine compounds show new intense absorptions in the region of 500–900 nm, and redshifted bands in the 250–400 nm region. By using DFT/time-dependent DFT calculations, the spin density and spectral features of both couples of precursors and PtII derivatives were investigated in terms of single-electron excitations between the Kohn–Sham orbitals of the optimized structures in the gas and condensed phases. A detailed comparison is allowed of the experimental and calculated spectral features of the neutral and 1– charged species.

Spectroscopic investigation of colloidal CdS quantum dots–methylene blue hybrid associates

Spectral properties of hydrophilic associates of colloidal CdS quantum dots (QDs) with methylene blue molecules (MB) prepared by sol–gel method have been studied. The two basic types of hybrid associates were found using FTIR spectra technique. The first-type associates are characterized by planar location of MB heterocycle on QDs spherical interface. In this case MB dimerization is not observed. Both nitrogen and sulfur heteroatoms and double =N+–(CH3)2 bonds of MB are participants of association which causes to conformation of MB heterocycle and π-conjugation length decrease. In UV–Vis absorption and luminescence spectra blue shift of MB peaks for QD-MB associates in comparison with MB spectra in solutions and gelatin was found. The second type of association mostly involves MB nitrogen heteroatoms and CdS QDs interface atoms. At the same time, peaks of UV–Vis and luminescence spectra are red shifted. In this case, dimerization manifestation of MB in QD-MB associates was found. Using the time correlated single photon counting technique resonance electronic excitation energy transfer from recombination luminescence center of CdS QDs to MB molecules was found. Its efficiency is in the range of 0.36–0.51.

Hydrogen conversion on non-magnetic insulating surfaces

Non-magnetic insulating catalysts are shown to be able to convert non-equilibrium mixtures of hydrogen by an electric mechanism. The molecular electrons feel the difference of temperature between the nuclei and the thermal bath, through their “Fermi” contact interaction, and consequently transfer the rotational angular momenta to the catalyst. This transfer, realized by the electrostatic interactions between the molecular and surface ionic electron clouds, is measured by non-diagonal exchange integrals. Our simple model of single-electron excitations interprets the experimental conversion rates recently observed on different surfaces (MOF or ASW) with different technics (infrared or ionization spectroscopy) and allows the study of the conversion rates in different contexts: thermal as well as transient, metallic or oxygen-induced, ion-molecule and molecule-molecule electron exchanges.

Raman-scattering measurements and theory of the energy-momentum spectrum for underdoped Bi2Sr2CaCuO(8+δ) superconductors: evidence of an s-wave structure for the pseudogap.

We reveal the full energy-momentum structure of the pseudogap of underdoped high-Tc cuprate superconductors. Our combined theoretical and experimental analysis explains the spectral-weight suppression observed in the B2g Raman response at finite energies in terms of a pseudogap appearing in the single-electron excitation spectra above the Fermi level in the nodal direction of momentum space. This result suggests an s-wave pseudogap (which never closes in the energy-momentum space), distinct from the d-wave superconducting gap. Recent tunneling and photoemission experiments on underdoped cuprates also find a natural explanation within the s-wave pseudogap scenario.

Z2fractionalized Chern/topological insulators in an exactly soluble correlated model

In this paper we propose an exactly soluble model in a two-dimensional honeycomb lattice, from which two phases are found. One is the usual Chern/topological insulating state and the other is an interesting ${Z}_{2}$ fractionalized Chern/topological insulator. While their bulk properties are similar, the edge states of physical electrons are quite different. The single electron excitation of the former shows a free particle like behavior while the latter one is gapped, which provides a definite signature to identify the fractionalized states. The transition between these two phases is found to fall into the three-dimensional Ising universal class. Significantly, near the quantum transition point the physical electron in the edge states shows strong Luttinger liquid behavior. An extension to the interesting case of the square lattice is also made. In addition, we also discuss some relationship between our exactly soluble model and various Hubbard-like models existing in the literature. The essential difference between the proposed ${Z}_{2}$ fractionalized Chern insulator and the hotly pursued fractional Chern insulator is also pointed out. The present work may be helpful for further study on the fractionalized insulating phase and related novel correlated quantum phases.