Lattice Motion Research Articles

Modeling surface motion effects in N2 dissociation on W(110): Ab initio molecular dynamics calculations and generalized Langevin oscillator model.

Accurately modeling surface temperature and surface motion effects is necessary to study molecule-surface reactions in which the energy dissipation to surface phonons can largely affect the observables of interest. We present here a critical comparison of two methods that allow to model such effects, namely, the ab initio molecular dynamics (AIMD) method and the generalized Langevin oscillator (GLO) model, using the dissociation of N2 on W(110) as a benchmark. AIMD is highly accurate as the surface atoms are explicitly part of the dynamics, but this advantage comes with a large computational cost. The GLO model is much more computationally convenient, but accounts for lattice motion effects in a very approximate way. Results show that, despite its simplicity, the GLO model is able to capture the physics of the system to a large extent, returning dissociation probabilities which are in better agreement with AIMD than static-surface results. Furthermore, the GLO model and the AIMD method predict very similar energy transfer to the lattice degrees of freedom in the non-reactive events, and similar dissociation dynamics.

Picosecond x-ray strain rosette reveals direct laser excitation of coherent transverse acoustic phonons.

Using a strain-rosette, we demonstrate the existence of transverse strain using time-resolved x-ray diffraction from multiple Bragg reflections in laser-excited bulk gallium arsenide. We find that anisotropic strain is responsible for a considerable fraction of the total lattice motion at early times before thermal equilibrium is achieved. Our measurements are described by a new model where the Poisson ratio drives transverse motion, resulting in the creation of shear waves without the need for an indirect process such as mode conversion at an interface. Using the same excitation geometry with the narrow-gap semiconductor indium antimonide, we detected coherent transverse acoustic oscillations at frequencies of several GHz.

Ferroelectric charge order enhanced by magnetic frustration in dimer Mott insulators

We investigate the effect of magnetic frustration on the dielectric properties of dimer Mott insulators. We adopt the two-dimensional quarter-filled extended Hubbard model for $\ensuremath{\kappa}\text{\ensuremath{-}}(\mathrm{BEDT}\text{\ensuremath{-}}\mathrm{TTF}){}_{2}X$ with an additional coupling with the dimer lattice motions, and numerically obtain the ground state. In the parameter range for strong magnetic frustration, an interdimer bond-length alternation mode that lifts the quasidegeneracy of classical spin configurations is strongly coupled to the electron system; this alternation mode occurs even with an extremely small electron-lattice coupling constant. Furthermore, the bond-length alternation induces in the dimers electric dipoles, which align along the same direction. A dimer Mott insulator phase with the ferroelectric charge order is obtained in the region. These results are consistent with the relaxorlike dielectric anomaly in $\ensuremath{\kappa}\text{\ensuremath{-}}{(\mathrm{BEDT}\ensuremath{-}\mathrm{TTF})}_{2}{\mathrm{Cu}}_{2}{(\mathrm{CN})}_{3}$.

Insight into the mechanism and outcoupling enhancement of excimer-associated white light generation.

Fundamental insight into excimer formation has been gained by using 9,10-bis[4-(9-carbazolyl)phenyl]anthracene] (Cz9PhAn) as a probe. Cz9PhAn exhibits a highly emissive blue fluorescence in solution and is found to emit a panchromatic white light spectrum (400-750 nm) in film, powder and single crystal, in which an additional excimer band appears at ∼550 nm. Detailed structural analyses, emission relaxation dynamics and a theoretical approach conclude the formation of an anthracene*/phenyl ring excimer through an overlap between π* (anthracene) and π (phenyl ring) orbitals in a face-to-edge stacking orientation. The rate of excimer formation is determined to be 2.2 × 109 s-1 at room temperature, which requires coupling with lattice motion with an activation energy of 0.44 kcal mol-1. Exploiting Cz9PhAn as a single emitter, a fluorescent white organic light emitting diode (WOLED) is fabricated with a maximum external quantum efficiency (ηext) of 3.6% at 1000 cd m-2 (4.2 V) and Commission Internationale de L'Eclairage (CIE) coordinates of (0.30, 0.33). The white-light Cz9PhAn reveals a preferred orientation of the transition dipole moment in the emitting layer to enhance light outcoupling. This non-doped, single component (Cz9PhAn) WOLED greatly reduces the complexity of the fabrication process, rendering a green and cost-effective alternative among the contemporary display/lighting technologies.

Reaction Rate Constants of CH4(ads) ⇌ CH3(ads) + H(ads) on Ni(111): The Effect of Lattice Motion.

Methane dissociation on metal surfaces is of great commercial importance. The dissociation and recombination rate constants of CH4 on Ni(111) are calculated using the quantum instanton approach with the path integral Monte Carlo method. The Ni(111) lattice is treated rigidly, classically, and quantum mechanically to reveal the effects of lattice motion and quantum tunneling. For the dissociation of CH4, the rates have the smallest value on the rigid lattice, while they possess the largest value on the quantum lattice. For instance, at 300 K, the rates on the classical and quantum lattices are 5 and 12 times larger than that on the rigid lattice, respectively. The curve of the Arrhenius plot for the dissociation rates on the rigid lattice demonstrates that the quantum tunneling effect of the ruptured H atom is remarkable, while the nearly invariable dissociation rates at low temperatures on the quantum lattice confirm that the thermally assisted tunneling should be dominant at low temperatures. For the recombination of CH4, the quantum lattice still has rates that are much larger than that of the rigid lattice. For instance, the ratio of the recombination rates on the quantum and rigid lattices is 12 at 300 K. The quantum tunneling effect seems to play a minor role in the recombination rates on the rigid lattice; however, the thermally assisted tunneling is still very significant for the recombination process.

Coherent phonon spectroscopy of non-fully symmetric modes using resonant terahertz excitation

We use intense terahertz (THz) frequency electromagnetic pulses generated via optical rectification in an organic crystal to drive vibrational lattice modes in single crystal Tellurium. The coherent modes are detected by measuring the polarization changes of femtosecond laser pulses reflecting from the sample surface, resulting in a phase-resolved detection of the coherent lattice motion. We compare the data to a model of Lorentz oscillators driven by the near-single-cycle broadband THz pulse. The demonstrated technique of optically probed coherent phonon spectroscopy with THz frequency excitation could prove to be a viable alternative to other time-resolved spectroscopic methods like standard THz time domain spectroscopy.

Electronic State-Resolved Electron-Phonon Coupling in an Organic Charge Transfer Material from Broadband Quantum Beat Spectroscopy.

The coupling of electron and lattice phonon motion plays a fundamental role in the properties of functional organic charge-transfer materials. In this Letter we extend the use of ultrafast vibrational quantum beat spectroscopy to directly elucidate electron-phonon coupling in an organic charge-transfer material. As a case study, we compare the oscillatory components of the transient reflection (TR) of a broadband probe pulse from single crystals of quinhydrone, a 1:1 cocrystal of hydroquinone and p-benzoquinone, after exciting nonresonant impulsive stimulated Raman scattering and resonant electronic transitions using ultrafast pulses. Spontaneous resonance Raman spectra confirm the assignment of these oscillations as coherent lattice phonon excitations. Fourier transforms of the vibrational quantum beats in our broadband TR measurements allow construction of spectra that we show report the ability of these phonons to directly modulate the electronic structure of quinhydrone. These results demonstrate how coherent ultrafast processes can characterize the complex interplay of charge transfer and lattice motion in materials of fundamental relevance to chemistry, materials sciences, and condensed matter physics.

Classification of collective modes in a charge density wave by momentum-dependent modulation of the electronic band structure

We present time- and angle-resolved photoemission spectroscopy measurements on the charge density wave system CeTe$_{3}$. Optical excitation transiently populates the unoccupied band structure and reveals a gap size of 2$\Delta$ = 0.59 eV. The occupied Te-5p band dispersion is coherently modified by three modes at $\Omega_{1}$ = 2.2 THz, $\Omega_{2}$ = 2.7 THz and $\Omega_{3}$ = 3 THz. All three modes lead to small rigid energy shifts whereas $\Delta$ is only affected by $\Omega_{1}$ and $\Omega_{2}$. Their spatial polarization is analyzed by fits of a transient model dispersion and DFT frozen phonon calculations. We conclude that the modes $\Omega_{1}$ and $\Omega_{2}$ result from in-plane ionic lattice motions, which modulate the charge order, and that $\Omega_{3}$ originates from a generic out-of-plane $A_{1g}$ phonon. We thereby demonstrate how the rich information from trARPES allows identification of collective modes and their spatial polarization, which explains the mode-dependent coupling to charge order.

Vibration band-gap properties of three-dimensional Kagome lattices using the spectral element method

The spectral element method (SEM) is extended to investigate the vibration band-gap properties of three-dimensional (3D) Kagome lattices. The dynamic stiffness matrix of the 3D element which contains bending, tensional and torsional components is derived. The spectral equations of motion of the whole 3D Kagome lattice are then established. Comparing with frequency-domain solutions calculated by the finite element method (FEM), the accuracy and the feasibility of the SEM solutions are verified. It can be shown that the SEM is suitable for analyzing the vibration band-gap properties. Due to the band-gap characteristics, the periodic 3D Kagome lattice has the performance of vibration isolation. The influences of the structural and material parameters on the vibration band-gaps are discussed and a new type of 3D Kagome lattice is designed to obtain the improved vibration isolation capability.

Ultrafast dynamics. Attosecond band-gap dynamics in silicon.

Electron transfer from valence to conduction band states in semiconductors is the basis of modern electronics. Here, attosecond extreme ultraviolet (XUV) spectroscopy is used to resolve this process in silicon in real time. Electrons injected into the conduction band by few-cycle laser pulses alter the silicon XUV absorption spectrum in sharp steps synchronized with the laser electric field oscillations. The observed ~450-attosecond step rise time provides an upper limit for the carrier-induced band-gap reduction and the electron-electron scattering time in the conduction band. This electronic response is separated from the subsequent band-gap modifications due to lattice motion, which occurs on a time scale of 60 ± 10 femtoseconds, characteristic of the fastest optical phonon. Quantum dynamical simulations interpret the carrier injection step as light-field-induced electron tunneling.

Molecular Cooling Fan: Factors for Optimization of Heat Dissipation Devices and Applications

A molecular cooling fan (MF) is a nanocomposite coating technology, where the quantized lattice motions in nanomaterials are assembled to absorb heat from the heat source, promote to higher vibration states, and emit excess energy by radiation. Using a factorial design technique, seven factors were investigated to optimize MF cooling performance and efficiency. The results show that a MF coating prepared with 8 nm sized multiwalled carbon nanotubes can cool down 4 °C lower than that assembled with 50–80 nm due to higher activity of lattice motions. The MF makes equilibrium temperature cool down by 10 and 20 °C at input operation voltages of 35 and 55 V on the same heat dissipation unit (HDU). Using the optimal factors, a MF coating was applied on commercial HDUs. The results demonstrated that molecular fan action can reduce the size and mass of the heat-sink module, offering a low cost LED light unit.

The Itô integral for Brownian motion in vector lattices: Part 2

The Itô integral for Brownian motion in a vector lattice, as constructed in Part 1 of this paper, is extended to accommodate a larger class of integrands. This extension provides an analogue of the indefinite Itô integral in the classical setting which yields a local martingale. The assumption is that there exists a conditional expectation operator on the vector lattice and the construction does not depend on a probability measure space. The classical case of the extended Itô integral is a special case of the constructed integral in the vector lattice.

Dissociative chemisorption of methane on Ni and Pt surfaces: mode-specific chemistry and the effects of lattice motion.

The dissociative chemisorption of methane on metal surfaces is of great practical and fundamental interest. Not only is it the rate-limiting step in the steam re-forming of natural gas, but also the reaction exhibits interesting mode-specific behavior and a strong dependence on the temperature of the metal. Electronic structure methods are used to explore this reaction on various Ni and Pt surfaces, with a focus on how the transition state is modified by motion of the metal lattice atoms. These results are used to construct models that explain the strong variation in reactivity with substrate temperature, shown to result primarily from changes in the dissociation barrier height with lattice motion. The dynamics of the dissociative chemisorption of CH4 on Ni and Pt is explored, using a fully quantum approach based on the reaction path Hamiltonian that includes all 15 molecular degrees of freedom and the effects of lattice motion. Agreement with experiment is good, and vibrational excitation of the molecule is shown to significantly enhance reactivity. The efficacy for this is examined in terms of the vibrationally nonadiabatic couplings, mode softening, mode symmetry, and energy localization in the reactive bond.

The Itô integral for Brownian motion in vector lattices: Part 1

In this paper the Itô integral for Brownian motion is constructed in a vector lattice and some of its properties are derived. The assumption is that there exists a conditional expectation operator on the vector lattice and the construction does not depend on a probability measure space. The classical case of the Itô integral is a special case of the constructed integral in the vector lattice.

Non-nuclear electron transport channels in hollow molecules

Electron transport in inorganic semiconductors and metals occurs through delocalized bands formed by overlapping electron orbitals. Strong correlation of electronic wave functions with the ionic cores couples the electron and lattice motions, leading to efficient interaction and scattering that degrades coherent charge transport. By contrast, unoccupied electronic states at energies near the vacuum level with diffuse molecular orbitals may form nearly-free-electron bands with density maxima in non-nuclear interstitial voids, which are subject to weaker electron-phonon interaction. The position of such bands typically above the frontier orbitals, however, renders them unstable with respect to electronic interband relaxation and therefore unsuitable for charge transport. Through electronic-structure calculations, we engineer stable, non-nuclear, nearly-free-electron conduction channels in low-dimensional molecular materials by tailoring their electrostatic and polarization potentials. We propose quantum structures of graphane-derived Janus molecular sheets with spatially isolated conducting and insulating regions that potentially exhibit emergent electronic properties, as a paradigm for molecular-scale non-nuclear charge conductors; we also describe tuning of their electronic properties by application of external fields and calculate their electron--acoustic-phonon interaction.

AC Quantum Interference Effects in Nanopatterned Nb Microstrips

The mixed-state dc voltage response of nanopatterned Nb microstrips is investigated by combined microwave (0.5 MHz—1 GHz) and dc electrical resistance measurements. The nanopatterns are arrays of symmetric grooves on the film surface fabricated by focused ion beam milling. They provide a pinning potential of the washboard type for the vortex motion. When subject to a microwave stimulus, the dc current–dc voltage curves of the microstrips exhibit Shapiro steps. The steps occur at voltages V=n V 0=n N f Φ 0, where n is an integer, N is the number of vortex rows between the voltage leads, f is the microwave frequency, and Φ 0 is the magnetic flux quantum. These steps arise as an interference effect when one or a multiple of the hopping period of the coherently moving Abrikosov vortices coincides with the period of the ac drive. When tuning the field value away from the matching field, the steps disappear due to lacking coherence in the motion of the Abrikosov vortex lattice. Dependencies of the dc critical (depinning) current on the microwave power and frequency are reported.

Physical mechanisms of coherent acoustic phonons generation by ultrafast laser action

In this review we address the microscopic mechanisms that are involved in the photogeneration processes of GHz–THz coherent acoustic phonons (CAP) induced by an ultrafast laser pulse. Understanding and describing the underlying physics is necessary indeed for improving the future sources of coherent acoustic phonons useful for the non-destructive testing optoacoustic techniques. Getting more physical insights on these processes also opens new perspectives for the emerging field of the opto-mechanics where lattice motions (surface and/or interfaces ultrafast displacements, nanostructures resonances) are controlled by light. We will then remind the basics of electron–phonon and photon-phonon couplings by discussing the deformation potential mechanism, the thermoelasticity, the inverse piezoelectric effect and the electrostriction in condensed matter. Metals, semiconductors and oxide materials will be discussed. The contribution of all these mechanisms in the photogeneration process of sound will be illustrated over several examples coming from the rich literature.

Time-dependent density functional theory of coupled electronic lattice motion in quasi-two-dimensional crystals

The existence of an acoustic plasmon in extrinsic (doped or gated) monolayer graphene was found recently in an {\it ab initio} calculation with the frozen lattice [M. Pisarra {\it et al.}, arXiv:1306.6273, 2013]. By the {\em fully dynamic} density-functional perturbation theory approach, we demonstrate a strong coupling of the acoustic plasmonic mode to lattice vibrations. Thereby, the acoustic plasmon in graphene does not exist as an isolated excitation, but it is rather bound into a combined plasmon-phonon mode. We show that the coupling provides a mechanism for the {\em bidirectional} energy exchange between the electronic and the ionic subsystems with fundamentally, as well as practically, important implications for the lattice cooling and heating by electrons in graphene.

Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)

We study the dynamics of transient hot H atoms on Pd(100) that originated from dissociative adsorption of H2. The methodology developed here, denoted AIMDEF, consists of ab initio molecular dynamics simulations that include a friction force to account for the energy transfer to the electronic system. We find that the excitation of electron-hole pairs is the main channel for energy dissipation, which happens at a rate that is five times faster than energy transfer into Pd lattice motion. Our results show that electronic excitations may constitute the dominant dissipation channel in the relaxation of hot atoms on surfaces.

Shearing transition in a superconducting vortex lattice subject to periodic pinning

We have studied the shearing forces in a superconducting vortex system with artificial pinning sites using the Corbino geometry. Current was injected into the center of a Nb disc and propagated radially outward to produce a force in the azimuthal direction on the vortices, with strength proportional to 1/$r$. We investigated the magnetoresistance properties of the vortex lattice as a function of temperature, current, and pinning lattice configuration. The measurements show steps instead of minima at the matching field positions, indicating an unexpected influence of the pinning array on the motion of the vortex lattice. The results imply that these steps are due to a shearing transition of the vortices.