Dynamics Of Electronic States Research Articles

Quantumness of electron transport in quantum dot devices through Leggett–Garg inequalities: A non-equilibrium Green’s function approach

Although coherent manipulation of electronic states can be achieved in quantum dot (QD) devices by harnessing nanofabrication tools, it is often hard to fathom the extent to which these nanoelectronic devices can behave quantum mechanically. Witnessing their nonclassical nature would thus remain of paramount importance in the emerging world of quantum technologies, since the coherent dynamics of electronic states plays there a crucial role. Against this backdrop, we resort to the general framework of Leggett-Garg inequalities (LGI) as it allows for distinguishing the classical and quantum transport through nanostructures by way of various two-time correlation functions. Using the local charge detection at two different time, we investigate here theoretically whether any quantum violation of the original LGI exists with varying device configurations and parameters under both Markovian and non-Markovian dynamics. Two-time correlators within LGI are derived in terms of the non-equilibrium Green’s functions (NEGFs) by exactly solving the quantum Langevin equations. The present study of non-Markovian dynamics of quantum systems interacting with reservoirs is significant for understanding the relaxation phenomenon in the ultrafast transient regime to especially mimic what happens to high-speed quantum devices. We can potentially capture the effect of finite reservoir correlation time by accounting for level-broadening at the electrodes along with non-Markovian memory effects. Furthermore, the large bias restriction is no longer imposed in our calculations so that we can safely consider a finite bias between the electronic reservoirs. Our approach is likely to open up new possibilities of witnessing the quantumness for other quantum many-body systems as well that are driven out of the equilibrium.

Dependent excited state absorption and dynamic of β-BF2 substituted metalloporphyrins: The metal ion effect

Absorption and relaxation dynamics of electronic states of free-base, Co(II), Cu(II) and Zn(II) porphyrins bearing a β-(2,2-difluoro-1,3,2-dioxaborinin-5-yl) group were investigated in dimethyl sulfoxide by using distinct time-resolved spectroscopic techniques. Furthermore, excited state absorption cross-section spectra were determined by combining white light continuum Z-Scan and transient absorption techniques. In the case of the free-base (2H) and Zn(II) porphyrins, we were able to quantify singlet–triplet conversion by analyzing the evolution of time-resolved fluorescence. Relaxation lifetimes from the excited to the ground state were observed in both porphyrins at nanosecond time scale. However, for Co(II) and Cu(II) metalloporphyrins it was observed in the picosecond time scale through femtosecond transient absorption, indicating that both compounds relax back to the ground state only by internal conversion processes. Co(II) and Cu(II) heavy atoms seem to prohibit the radiative and intersystem crossing processes.

Vibronic coupling in the first six electronic states of pentafluorobenzene radical cation: Radiative emission and nonradiative decay

Nuclear dynamics in the first six vibronically coupled electronic states of pentafluorobenzene radical cation is studied with the aid of the standard vibronic coupling theory and quantum dynamical methods. A model 6 × 6 vibronic Hamiltonian is constructed in a diabatic electronic basis using symmetry selection rules and a Taylor expansion of the elements of the electronic Hamiltonian in terms of the normal coordinate of vibrational modes. Extensive ab initio quantum chemistry calculations are carried out for the adiabatic electronic energies to establish the diabatic potential energy surfaces and their coupling surfaces. Both time-independent and time-dependent quantum mechanical methods are employed to perform nuclear dynamics calculations. The vibronic spectrum of the electronic states is calculated, assigned, and compared with the available experimental results. Internal conversion dynamics of electronic states is examined to assess the impact of various couplings on the nuclear dynamics. The impact of increasing fluorination of the parent benzene radical cation on its radiative emission is examined and discussed.

Spin Resonance in a Quantum Dot at the Edge of a Topological Insulator with the Inclusion of Continuum States

The dynamics of electronic states under the action of a periodic electric field applied to a quantum dot created by magnetic barriers at the one-dimensional edge of a two-dimensional topological insulator based on a HgTe/CdTe quantum well has been studied. A configuration with two discrete levels is considered and transitions to continuum states above barriers are taken into account. The frequency of oscillations of the discrete level populations has been calculated for various field amplitudes. It has been shown numerically and analytically that the inclusion of the continuous spectrum leads to a decrease in the total population of discrete levels in time. The characteristic times of this decrease corresponding to transitions to continuum have been determined. The dynamics of average values of the energy, spin projections, coordinates, local probability density, and local spin density has been calculated. Time-averaged local probability density current that describes the quantum dot escape at transitions to the continuous spectrum has been calculated. The results of this work can be useful for the design of new generations of nanoelectronics and spintronics devices based on topological insulators.

Electronic structure and spectroscopy of the low-lying electronic states of antimony hydride

The electronic structure and spectroscopic properties of antimony hydride(SbH) have been investigated based on high-level ab initio calculations by utilizing the internally contracted multi-reference configuration interaction plus the Davidson correction(icMRCI+Q) method. The core-valence correlation (CV) and spin–orbit coupling (SOC) effect are considered. The potential energy curves of the 12 Λ-S states as well as the 25 Ω states that split from them via SOC effect are obtained. The spectroscopic constants of bound states are determined and well reproduced the results of the available experimental and theoretical studies. The SOC induced predissociation mechanisms of the A3Π state have been analyzed with the aid of the spin−orbit matrix element. The transition dipole moments, Franck-Condon factors, and the radiative lifetimes of the a2-X21 and b0+- X3Σ− transitions have been reported. Our study is expected to be helpful for understanding the spectroscopy and dynamics of electronic states of the SbH molecule.

Higher Order Vibronic Sidebands of Chlorophyll a and Bacteriochlorophyll a for Enhanced Excitation Energy Transfer and Light Harvesting.

Optical absorption and fluorescence spectra of molecules in condensed phases often show extensive sidebands. Originating from electron-vibrational and electron-phonon couplings, these spectral tails bear important information on the dynamics of electronic states and processes the molecules are involved in. The vibronic sidebands observed in conjugate Qy absorption and fluorescence spectra of chlorophyll a and bacteriochlorophyll a are relatively weak, characterized by the total Huang-Rhys factor which is less than one. Therefore, it is widely considered that only fundamental intramolecular modes are responsible for their formation. Here, we provide evidence for extra-long and structured fluorescence tails of chlorophyll a and bacteriochlorophyll a as far as 4000 cm-1 from respective spectral origins, far beyond the frequency range of fundamental modes. According to quantum chemical simulations, these sidebands extending to ∼960 nm in chlorophyll a and ∼1140 nm in bacteriochlorophyll a into the infrared part of the optical spectrum are mainly contributed to by vibrational overtones of the fundamental modes. Because energy transfer and relaxation processes generally depend on vibronic overlap integrals, these findings potentially contribute to better understanding of many vital photo-induced phenomena, including photosynthetic light harvesting.

Multistep and multiscale electron transfer and localization dynamics at a model electrolyte/metal interface.

The lifetime, coupling, and localization dynamics of electronic states in molecular films near metal electrodes fundamentally determine their propensity to act as precursors or reactants in chemical reactions, crucial for a detailed understanding of charge transport and degradation mechanisms in batteries. In the current study, we investigate the formation dynamics of small polarons and their role as intermediate electronic states in thin films of dimethyl sulfoxide (DMSO) on Cu(111) using time- and angle-resolved two-photon photoemission spectroscopy. Upon photoexcitation, a delocalized DMSO electronic state is initially populated two monolayers from the Cu surface, becoming a small polaron on a 200 fs time scale, consistent with localization due to vibrational dynamics of the DMSO film. The small polaron is a precursor state for an extremely long-lived and weakly coupled multilayer electronic state, with a lifetime of several seconds, thirteen orders of magnitude longer than the small polaron. Although the small polaron in DMSO has a lifetime of 140 fs, its role as a precursor state for long-lived electronic states could make it an important intermediate in multistep battery reactivity.

Dynamics of Electronic States and Magnetoabsorption in 3D Topological Insulators in a Quantizing Magnetic Field

Quantum states have been calculated analytically; the dynamics of a wave packet in a magnetic field has been investigated, and the optical absorption coefficient has been calculated for surface states in 3D topological insulators of the Bi2Te3 family. We have detected a qualitative effect of the hexagonal warping of the spectrum on the structure of wavefunctions at the Landau levels, its manifestation in the features of the wave packet dynamics in a quantizing magnetic field, as well as in the frequency dependence of the optical absorption coefficient, in which new peaks that are absent in the isotropic model of the spectrum appear depending on the polarization of the incident wave. The effects considered here can be manifested in the optical and transport experiments with topological insulators, which makes it possible to determine the parameters of their band structure.

Harnessing Molecular Vibrations to Probe Triplet Dynamics During Singlet Fission.

Ultrafast vibrational spectroscopy in the mid-infrared spectral range provides the opportunity to probe the dynamics of electronic states involved in all stages of the singlet fission reaction through their unique vibrational frequencies. This capability is demonstrated using a model singlet fission chromophore, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). The alkyne groups of the TIPS side chains are coupled to the conjugated framework of the pentacene cores, enabling direct examination of the dynamics of triplet excitons that have successfully separated from correlated triplet pair states in crystalline films of TIPS-Pn. Relaxation processes during the separation of triplet excitons and triplet-triplet annihilation after their separation result in the formation of hot ground state molecules that also exhibit unique vibrational frequencies. Because all organic molecules possess native vibrational modes, ultrafast vibrational spectroscopy offers a new approach to examine the dynamics of electronic intermediates that may inform ongoing efforts to utilize singlet fission to overcome thermalization losses in photovoltaic applications.

Electronic States of Difluorocarbene Calculated by Multireference Configuration Interaction Method**Supported by the 2014 Postdoctoral Sustentation Fund of Qingdao under Grant No 01020120517, the Natural Science Foundation of Shandong Province under Grant No ZR2014AP001, the National Natural Science Foundation of China under Grant No 11447226, and the Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents under

We investigate the geometries and energies of seven electronic states and of CF2 carbene using internally contracted multireference configuration interaction methods including Davidson correction (icMRCI+Q) with different basis sets aug-cc-pVXZ (X=T, Q, 5). For the first time, the potential energy curves of electronic states of CF2 related to the lowest dissociation limit are calculated at the icMRCI+Q/aug-cc-pVTZ level. The ab initio results will further increase our understanding of the structures and dynamics of electronic states of CF2 radical.

Simulating Excited State Dynamics in Systems with Multiple Avoided Crossings Using Mapping Variable Ring Polymer Molecular Dynamics.

Mapping variable ring polymer molecular dynamics (MV-RPMD) is an approximate quantum dynamics method based on imaginary-time path integrals for simulating electronically nonadiabatic photochemical processes. By employing a mapping protocol to transform from a discrete electronic state basis to continuous Cartesian phase-space variables, the method captures electronic state transitions coupled to nuclear motion using only classical MD trajectories. In this work, we extend the applicability of MV-RPMD to simulations of photoinduced excited electronic state dynamics in nonadiabatic systems with multiple avoided crossings. We achieve this by deriving a new electronic state population estimator in the phase space of electronic variables that is exact at equilibrium and numerically accurate in real time. Further, we introduce an efficient constraint protocol to initialize an MV-RPMD simulation to a particular electronic state. We numerically demonstrate the accuracy of this estimator and constraint technique in describing electronic state dynamics from an initial nonequilibrium state in six model systems, three of which describe photodissociation.

Multireference configuration interaction study of dichlorocarbene

Dichlorocarbene is an important reactive chemical intermediate, which has received much investigation. However, the energy, structure, and dynamics of the excited states are not well understood. Here, we investigated the equilibrium geometries and energies of seven electronic states, X̃1A1, Ã1B1, ã3B1, B̃1A2, b̃3A2, C̃1B2 and c̃3B2 of CCl2 using internally contracted multireference configuration interaction method including Davidson correction (icMRCI+Q) with different basis sets aug-cc-pV(X+d)Z(X=T,Q,5), and the effects of different basis sets on the geometries and energies. For the first time, the theoretical studies of high excited singlet and triplet states of CCl2 that are related to the lowest three dissociation limits were carried out at the icMRCI+Q/aug-cc-pV(5+d)Z level. The results were compared with the previous experimental and theoretical data where available. Our results will add some understanding and shed some light on the structures and dynamics of electronic states of CCl2 radical.

Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ππ* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron tetraphenyl porphyrin chloride (Fe((III))TPPCl) exhibits picosecond decay to a metal centered d → d* (4)T state. This state decays on a ca. 16 ps time scale in room temperature solution but persists for much longer in a cryogenic glass. The photoreactivity of the (4)T state may lead to novel future applications for these compounds. In contrast, the nonplanar cob(III)alamins contain two axial ligands to the central cobalt atom. The upper axial ligand can be an alkyl group as in the two biologically active coenzymes or a nonalkyl ligand such as -CN in cyanocobalamin (vitamin B12) or -OH in hydroxocobalamin. The electronic structure, energy cascade, and bond cleavage of these compounds is sensitive to the details of the axial ligand. Nonalkylcobalamins exhibit ultrafast internal conversion to a low-lying state of metal to ligand or ligand to metal charge transfer character. The compounds are generally photostable with ground state recovery complete on a time scale of 2-7 ps in room temperature aqueous solution. Alkylcobalamins exhibit ultrafast internal conversion to an S1 state of d/π → π* character. Most compounds undergo bond cleavage from this state with near unit quantum yield within ∼100 ps. Recent theoretical calculations provide a potential energy surface accounting for these observations. Conformation dependent mixing of the corrin π and cobalt d orbitals plays a significant role in the observed photochemistry and photophysics.

An ab Initio Investigation of Fluorobromo Carbene

Fluorobromo carbene, an important halogenated carbene in the stratospheric ozone depletion, has long been received considerable interest. However, the energy, structure, and dynamics of even the lowest excited states have not been well understood. In this paper, we performed a detail ab initio study on CFBr using complete active space second-order perturbation (CASPT2) and multireference configuration interaction (MRCI) method. We investigated the effect of basis set on the CASPT2 results of the ground X(1)A' state and the first excited singlet A(1)A" state. The potential energy surface (PES) of the A(1)A" state along C-Br bond distance was carefully examined at CASPT2/cc-pV5Z level, by optimizing C-F bond and F-C-Br angle at every C-Br bond length in contrast to fix them at the equilibrium values. On the basis of the PES, a reliable barrier height of the A(1)A" state was obtained from CASPT2 and MRCI+Q calculations with different basis sets, considering the scalar relativistic effect, spin-orbit coupling, and core-valence correlation. Finally, we carried out the first theoretical study on higher excited state with energy up to 7 eV. The present calculated results were compared with previous experimental and theoretical results where available. Our results will add some understanding and shed more light on the structure and dynamics of electronic states of CFBr radical.

Charge Separation and Recombination in CdTe/CdSe Core/Shell Nanocrystals as a Function of Shell Coverage: Probing the Onset of the Quasi Type-II Regime

Femtosecond transient absorption (TA) is used to investigate population dynamics of electronic states in CdTe/CdSe core/shell nanocrystals (NCs) with varying CdSe shell coverage. Upon CdSe shell growth, the CdTe/CdSe NCs show a gradual evolution of surface passivation toward a quasi-type-II charge separation regime. Our results indicate that ultrafast electron transfer (ET) through the interface of CdTe/CdSe NCs becomes measurable as the CdSe shell approaches the quasi-type-II regime which we experimentally determined to be at 0.4 nm (shell) for a 3.4 nm CdTe core. This work reports the first measurement using femtosecond TA to study the electronic states in CdTe/CdSe NCs and spectroscopically observe the evolution of an ultrafast charge transfer (CT) in such a core/shell system. Time-resolved photoluminescence (PL) spectroscopy is used to study the radiative lifetimes of the CdTe/CdSe NCs. One monolayer CdSe coverage leads to longer-lived PL, which is red-shifted by 140 nm compared to the CdTe core PL. I...

Femtosecond dynamics of electronic states in the Mott insulator 1T-TaS2 by time resolved photoelectron spectroscopy

Photoexcitation of the Mott insulator 1T-TaS2 by an intense laser pulse leads to an ultrafast transition toward a gapless phase. Besides the collapse of the electronic gap, the sudden excitation of the charge density wave (CDW) mode results in periodic oscillations of the electronic states. We employ time resolved photoelectron spectroscopy to monitor the rich dynamics of electrons and phonons during the relaxation toward equilibrium. The qualitative difference between the oscillatory dynamics of the CDW and the monotonic recovery of the electronic gap proves that 1T-TaS2 is indeed a Mott insulator. Moreover the quasi-instantaneous build-up of mid gap states is in contrast with the retarded response expected from a Peierls insulating phase. Interestingly, the photoinduced electronic states in the midgap spectral region display a weak resonance that is reminiscent of a quasiparticle peak.

Entanglement of electronic states of impurities in a nanocrystal

It is shown that the dynamics of electronic states of impurities in a nanocrystal embedded in a bulk matrix can be described with the help of the model of a single-mode microcavity with quasi-resonant atoms and losses at the mirrors. In the proposed model, the dynamics of impurities is similar to the collective decay of atoms in a common bath. In the case of a nanocrystal, matrix phonons represent this bath. Impurities interact with the localized phonon mode of the nanocrystal owing to the electron-phonon interaction. The localized phonon mode is coupled with bath phonons at the nanocrystal boundary. In the dispersive limit, the standard model of collective relaxation appears, within the framework of which, different types of many-particle entangled electronic states of impurities are described. In the case of exact resonance, similar entangled states also appear, which are discussed for two impurities in a nanocrystal.

Dynamics of Electronic States and Spin−Flip for Photodissociation of Dihalogens in Matrices: Experiment and Semiclassical Surface-Hopping and Quantum Model Simulations for F2 and ClF in Solid Ar

Three approaches are combined to study the electronic states' dynamics in the photodissociation of F(2) and ClF in solid argon. These include (a) semiclassical surface-hopping simulations of the nonadiabatic processes involved. These simulations are carried out for the F(2) molecule in a slab of 255 argon atoms with periodic boundary conditions at the ends. The full manifold of 36 electronic states relevant to the process is included. (b) The second approach involves quantum mechanical reduced-dimensionality models for the initial processes induced by a pump laser pulse, which involve wavepacket propagation for the preoriented ClF in the frozen argon lattice and incorporate the important electronic states. The focus is on the study of quantum coherence effects. (c) The final approach is femtosecond laser pump-probe experiments for ClF in Ar. The combined results for the different systems shed light on general properties of the nonadiabatic processes involved, including the singlet to triplet and intertriplet transition dynamics. The main findings are (1) that the system remains in the initially excited-state only for a very brief, subpicosecond, time period. Thereafter, most of the population is transferred by nonadiabatic transitions to other states, with different time constants depending on the systems. (2) Another finding is that the dynamics is selective with regard to the electronic quantum numbers, including the Lambda and Omega quantum numbers, and the spin of the states. (3) The semiclassical simulations show that prior to the first "collision" of the photodissociated F atom with an Ar atom, the argon atoms can be held frozen, without affecting the process. This justifies the rigid-lattice reduced-dimensionality quantum model for a brief initial time interval. (4) Finally, degeneracies between triplets and singlets are fairly localized, but intertriplet degeneracies and near degeneracies can span an extensive range. The importance of quantum effects in photochemistry of matrix-isolated molecules is discussed in light of the results.

Conical intersections in solution: non-equilibrium versus equilibrium solvation

In this contribution we discuss some dynamical properties of a recently proposed protonated Schiff base model to study the solvation effect on conical intersection (CI) dynamics [I. Burghardt, L. S. Cederbaum, and J. T. Hynes, Faraday Discuss. 127, 395 (2004)]. We consider two dynamical solvation regimes: equilibrium and non-equilibrium. In the first regime, the solvent instantaneously equilibrates to the evolving solute charge distribution, an assumption of many schemes for quantum chemical calculations in solution. In the second regime, appropriate for describing the actual dynamics, account is taken of the (inertial) dynamics of the solvent electrical polarization field. In this regime, both the excited electronic state dynamics and the non-adiabatic transitions in the CI region leading from the excited state to the ground electronic state, calculated via a surface hopping method, are found to differ significantly from those which follow from an equilibrium solvation characterization. Nonetheless, an equilibrium solvation description is useful in locating the seam of CIs which results from the chromophore–solvent interaction.

A femtosecond time-resolved investigation of dual fluorescence from N6,N6-dimethyladenine

The excited electronic state dynamics of N(6),N(6)-dimethyladenine (DMAde), a molecule known to emit dual fluorescence, has been studied in aqueous solution using femtosecond fluorescence up-conversion spectroscopy. Time profiles of the fluorescence of DMAde excited at lambda= 258 nm were measured at a series of wavelengths in the range 320 nm <or=lambda(fl)<or= 650 nm. At wavelengths in the near UV (lambda(fl)<or= 420 nm), the time profiles were dominated by a very short-lived decay component with a lifetime between 0.2 ps <or=tau(1)<or= 0.6 ps, depending on the detection wavelength. Two other components with lifetimes of tau(2) approximately 3.5 ps and tau(3) approximately 60 ps gave minor contributions. In the emission observed at longer wavelengths (lambda(fl)>or= 500 nm), which appeared slightly delayed compared to the UV fluorescence, the long-lived fluorescence component (tau(3)) dominated, the second component (tau(2)) disappeared. The results are consistent with the assumption that DMAde is primarily excited to a short-lived local excited (LE) electronic state that fluoresces mostly in the UV and decays rapidly, on a approximately 0.5 ps timescale, to an intramolecular charge transfer (ICT) state that emits only at longer wavelengths in the visible spectrum. The fluorescence-time profiles and transient fluorescence spectra reconstructed from the time profiles provided further information on secondary relaxation processes within and between the excited states and their non-radiative relaxation to the electronic ground state.