Spin-phonon dispersion in magnetic materials.

Microscopic coupling between the electron spin and the lattice vibration is responsible for an array of exotic properties from morphic effects in simple non magnets to magnetodielectric coupling in multiferroic spinels and hematites. Traditionally, a single spin-phonon coupling constant is used to characterize how effectively the lattice can affect the spin, but it is hardly enough to capture novel electromagnetic behaviors to the full extent. Here, we introduce a concept of spin-phonon dispersion to project the spin moment change along the phonon crystal momentum direction, so the entire spin change can be mapped out. Different from the phonon dispersion, the spin-phonon dispersion has both positive and negative frequency branches even in the equilibrium ground state, which correspond to the spin enhancement and spin reduction, respectively. Our study of bcc Fe and hcp Co reveals that the spin force matrix, that is, the second-order spatial derivative of spin moment, is similar to the vibrational force matrix, but its diagonal elements are smaller than the off-diagonal ones. This leads to the distinctive spin-phonon dispersion. The concept of spin-phonon dispersion expands the traditional Elliott-Yafet theory in nonmagnetic materials to the entire Brillouin zone in magnetic materials, thus opening the door to excited states in systems such as CoF2and NiO, where a strong spin-lattice coupling is detected in the THz regime.

Lattice Vibrations and Time-Dependent Evolution of Local Phonon Modes during Exciton Formation in Conjugated Polymeric Molecules.

Based on nonadiabatic molecular dynamics that integrate electronic transitions with the time-dependent phonon spectrum, this article provides a panoramic landscape of the dynamical process during the formation of photoinduced excitons in conjugated polymers. When external optical beam/pulses with intensities of 10 µJ/cm2 and 20 µJ/cm2 are utilized to excite a conjugated polymer, it is found that the electronic transition firstly triggers local lattice vibrations, which not only locally distort alternating bonds but change the phonon spectrum as well. Within the first 60 fs, the occurrence of local distortion of alternating bonds accompanies the localization of the excited-state's electron. Up to 100 fs, both alternating bonds and the excited electronic state are well localized in the middle of the polymer chain. In the first ~200 fs, the strong lattice vibration makes a local phonon mode at 1097.7 cm-1 appear in the phonon spectrum. The change of electron states then induces the self-trapping effect to act on the following photoexcitation process of 1.2 ps. During the following relaxation of 1.0 ps, new local infrared phonon modes begin to occur. All of this, incorporated with the occurrence of local infrared phonon modes and localized electronic states at the end of the relaxation, results in completed exciton formation.

Charge Accumulation of Amplified Spontaneous Emission in a Conjugated Polymer Chain and Its Dynamical Phonon Spectra.

In this article, the detailed photoexcitation dynamics which combines nonadiabatic molecular dynamics with electronic transitions shows the occurrence of amplified spontaneous emission (ASE) in conjugated polymers, accompanied by spontaneous electric polarization. The elaborate molecular dynamic process of ultrafast photoexcitation can be described as follows: Continuous external optical pumping (laser of 70 µJ/cm2) not only triggers the appearance of an instantaneous four-level electronic structure but causes population inversion for ASE as well. At the same time, the phonon spectrum of the conjugated polymer changes, and five local infrared lattice vibrational modes form at the two ends, which break the original symmetry in the system and leads to charge accumulation at the ends of the polymer chain without an external electric field. This novel phenomenon gives a brand-new avenue to explain how the lattice vibrations play a role in the evolution of the stimulated emission, which leads to an ultrafast effect in solid conjugated polymers.

Photoexcitation-induced local phonon spectra and local hot excitons in polymer solar cells.

In this article, based on nonadiabatic molecular dynamics with electronic transitions, the elaborate ultrafast process of hot excitons in conjugated polymer solar cells is revealed. When an external optical beam/pulse with the intensity of 30 µJ/cm-2 is utilized to excite a conjugated polymer, just within only 50 fs, the electronic transition not only redistributes the electron population in the original molecular orbital, but also starts to localize the electron cloud of excited states and to distort the alternating bonds in the polymer chain. Up to 300 fs, the lattice distortion has been stabilized. During the formation of hot excitons, the prominent self-trapping effect of conjugated polymer triggers the occurrence of local infrared active phonon modes, with five peaks in the phonon spectrum as the hot excitons relax. The characteristic phonon spectrum and infrared modes hence form the fingerprint of the hot excitons of a conjugated polymer, which are readily distinguished from other excitation states in the polymer.

Asymptotic dynamics of three-dimensional bipolar ultrashort electromagnetic pulses in an array of semiconductor carbon nanotubes.

We study the propagation of three-dimensional bipolar ultrashort electromagnetic pulses in an array of semiconductor carbon nanotubes at times much longer than the pulse duration, yet still shorter than the relaxation time in the system. The interaction of the electromagnetic field with the electronic subsystem of the medium is described by means of Maxwell's equations, taking into account the field inhomogeneity along the nanotube axis beyond the approximation of slowly varying amplitudes and phases. A model is proposed for the analysis of the dynamics of an electromagnetic pulse in the form of an effective equation for the vector potential of the field. Our numerical analysis demonstrates the possibility of a satisfactory description of the evolution of the pulse field at large times by means of a three-dimensional generalization of the sine-Gordon and double sine-Gordon equations.

Breaking of lattice potential well-induced confinement of carriers in conjugated polymers.

Recent experimental research has reported that a surface electric field on the polymer solar cell can restrain the recombination of the resultant charged carriers [23]. Based on this, this article reveals an underlying mechanism: If a surface electric field below 4.5 × 104 V/cm is applied to the polymer layer, the electric field drives the charged polaron to transport. Once the polaron approaches and collides with the exciton, it is easily trapped by the potential well produced by the exciton and then forms a charged exciton. The decay of the resultant charged exciton rapidly reduces the number of excitons. However, once the external field surpasses the threshold value of 4.5 × 104 V/cm, the charged polaron absorbs momentum from the external electric field and shakes off the trapping of the exciton. It finally steps out of the original lattice potential well, where the appropriate electric field magnitude ranges from 5.5 × 104 V/cm to 8 × 105 V/cm. After a collision of 300 fs, apart from a phase shift, the exciton still exists. Then, the originally carriers is dissociated when the electric field reaches 0.8 MV/cm. The applied surface field is able to effectively keep the excitons from fusion with the transporting charged polarons, which provides a valid and easily manufactured approach to yield higher efficiency of polymer solar cells.

Transient Aspects and Ultrafast Dynamical Processes of Amplified Spontaneous Emission in Conjugated Polymers.

Experimental research has revealed that the stimulated emission in organic semiconductors is associated with lattice vibrations. To reveal the dynamical aspects of the excited state of the conjugated polymer, the electron-transition process has been incorporated into the molecular dynamics, making it possible to simulate in detail the whole ultrafast process of amplified spontaneous emission (ASE). A typical conjugated polymer, poly( p-phenylene vinylene), is chosen as a model for the research. When an external laser beam of 60 µJ/cm2 is applied to photoexcite the polymer, the energy levels begin to oscillate within 100 fs. Thanks to the prominent self-trapping effect of the conjugated polymer, the laser beam also drives the lattice of the polymer chain to strongly vibrate. Until about 200 fs, four energy levels are pulled to the center of the energy gap, resulting in a transient discrete four-energy-level electronic structure for ASE. Simultaneously, in this ultrafast dynamical process, within the first 1 ps, inversion of the electron population occurs along with the appearance of a localized electronic cloud and locally distorted alternating bonds of the polymer chain. This detailed description of the whole ultrafast process of ASE helps in the understanding of the microscopic dynamical evolution of excitation in conjugated polymers.

Laser-induced ultrafast transport and demagnetization at the earliest time: first-principles and real-time investigation.

It is generally believed that there are at least two ways to use an ultrafast laser pulse to demagnetize a magnetic sample. One is to directly photo-demagnetize the system through spin-orbit coupling (SOC), and the other is to utilize ultrafast hot electron transport without SOC. The challenge is that these two processes are entangled on the same time scale. While the experimental results have been inconclusive, theoretical investigations are even scarcer, beyond those earlier studies based on spin superdiffusion. For instance, we do not even know how fast electrons move under laser excitation and how far they move. Here we carry out a first-principles time-dependent calculation to investigate how fast electrons actually move under laser excitation and how large the electron transport affects demagnetization on the shortest time scale. To take into account the transport effect, we implement the intraband transition in our theory. In the bulk fcc Ni, we find the effect of the spin transport on the demagnetization is extremely small, no more than 1%. The collective electron velocity in Ni is 0.4 Å fs-1, much smaller than the Fermi velocity, and the collective displacement is no more than 0.1 Å. But this does not mean that electrons do not travel fast; instead we find that electron velocities at two opposite crystal momenta cancel each other. We follow the Γ-X line and find a huge dispersion in the velocities in the crystal momentum space. In the Fe/W(1 1 0) thin film, the overall demagnetization is larger than Ni, and the Fermi velocity is higher than Ni. However, the effect of the spin transport is still small in the Fe/W(1 1 0) thin film. Based on our numerical results and existing experimental findings, we propose a different mechanism that can explain two latest experimental results. Our finding sheds new light on the effect of ballistic transport on demagnetization.

Generating high-order optical and spin harmonics from ferromagnetic monolayers.

High-order harmonic generation (HHG) in solids has entered a new phase of intensive research, with envisioned band-structure mapping on an ultrashort time scale. This partly benefits from a flurry of new HHG materials discovered, but so far has missed an important group. HHG in magnetic materials should have profound impact on future magnetic storage technology advances. Here we introduce and demonstrate HHG in ferromagnetic monolayers. We find that HHG carries spin information and sensitively depends on the relativistic spin-orbit coupling; and if they are dispersed into the crystal momentum k space, harmonics originating from real transitions can be k-resolved and carry the band structure information. Geometrically, the HHG signal is sensitive to spatial orientations of monolayers. Different from the optical counterpart, the spin HHG, though probably weak, only appears at even orders, a consequence of SU(2) symmetry. Our findings open an unexplored frontier-magneto-high-order harmonic generation.

Conjugation of Nanomaterials and Nematic Liquid Crystals for Futuristic Applications and Biosensors.

The established role of nematic liquid crystals (NLCs) in the recent rapid development of displays has motivated researchers to modulate the electro-optical properties of LCs. Furthermore, adding nanomaterials into NLCs has led to enhancements of the properties of NLCs, like reduced threshold of the operating voltage, variation in pretilt angle, reduced switching time, etc. These enhanced properties, due to interfacial dynamics, are enabling wider applications of NLCs and nanomaterials. The recent literature of nanomaterial-doped NLCs is rich with various kinds of nanomaterials in a variety of NLCs. The light has been focused on the most widely used and studied gold nanoparticles in NLCs. The intrinsic inherent property of easy excitation of surface plasmons polaritons (SPP) is the mediating interaction of NLC electric dipoles and the polarization of charges in the GNP surface. The concepts and methods for the application of metal nanomaterials as dopants in NLCs are discussed for future applications, especially biosensors. The biosensing application of NLCs alone has already been proven in the literature. However, it is always desirable to further enhance the detection efficiency and selectivity, which have been achieved by the conjugation of GNPs and nickel nanoparticles with NLCs and their compatibility with biological materials. This aspect of future application of nanoparticles and NLC makes the point more selective to be included in the present manuscript.

Ultrafast optical pulse convertor caused by oscillations of the energy level structure in the conjugated polymer poly(p-phenylenevinylene).

For a conjugated polymer irradiated by two optical pulses, the whole process of excitation, involving lattice oscillations, oscillations of the energy level structure, and evolution of the electron cloud, is investigated. Localization of the electron cloud appears in the first 100 fs of irradiation, which in turn induces vibrations of lattice of the polymer chain as well as oscillations of the band gap. These oscillations filter the absorption of the external optical field inversely and convert the original optical field to an ultrafast light field whose intensity varies with a certain period. Based on the mechanism, oscillations of the energy level structure, induced by the external excitation, can be designed as an ultrafast response optical convertor that is able to change the external optical pulse into a new effective light field with a certain oscillation period. This helps provide new insight into designing nanostructures for polymeric optoelectronics.

Is perpendicular magnetic anisotropy essential to all-optical ultrafast spin reversal in ferromagnets?

All-optical spin reversal presents a new opportunity for spin manipulations, free of a magnetic field. Most of all-optical-spin-reversal ferromagnets are found to have a perpendicular magnetic anisotropy (PMA), but it has been unknown whether PMA is necessary for spin reversal. Here we theoretically investigate magnetic thin films with either PMA or in-plane magnetic anisotropy (IMA). Our results show that spin reversal in IMA systems is possible, but only with a longer laser pulse and within a narrow laser parameter region. Spin reversal does not show a strong helicity dependence where the left- and right-circularly polarized light lead to the identical results. By contrast, the spin reversal in PMA systems is robust, provided both the spin angular momentum and laser field are strong enough while the magnetic anisotropy itself is not too strong. This explains why experimentally the majority of all-optical spin-reversal samples are found to have strong PMA and why spins in Fe nanoparticles only cant out of plane. It is the laser-induced spin-orbit torque that plays a key role in the spin reversal. Surprisingly, the same spin-orbit torque results in laser-induced spin rectification in spin-mixed configuration, a prediction that can be tested experimentally. Our results clearly point out that PMA is essential to spin reversal, though there is an opportunity for in-plane spin reversal.

Nanotherapy of cancer by photoelectrons emitted from the surface of nanoparticles exposed to nonionizing ultraviolet radiation.

AIM: We introduce a new method for selectively destroying cancer cell organelles by electrons emitted from the surface of intracellularly localized nanoparticles exposed to the nonionizing ultraviolet (UV) radiation. METHODS: We propose to target cancerous intracellular organelles by nanoparticles and expose them to UV radiation with energy density safe for healthy tissue. RESULTS: We simulate the number of photoelectrons produced by the nanoparticles made of various metals and radii, calculate their kinetic energy and compare it to the threshold energy for producing biological damage. CONCLUSION: Exposure of metal nanoparticles to UV radiation generates photoelectrons with kinetic energies up to 11 eV, which is high enough to produce single- to double-strand breaks in the DNA and damage the cancerous cell organelles.

Ultrafast reduction of exchange splitting in ferromagnetic nickel.

A decade ago Rhie et al (2003 Phys. Rev. Lett. 90 247201) reported that when ferromagnetic nickel is subject to an intense ultrashort laser pulse, its exchange splitting is reduced quickly. But to simulate such reduction remains a big challenge. The popular rigid band approximation (RBA), where both the band structure and the exchange splitting are held fixed before and after laser excitation, is unsuitable for this purpose, while the time-dependent density functional theory could be time-consuming. To overcome these difficulties, we propose a time-dependent Liouville and density functional theory (TDLDFT) that integrates the time-dependent Liouville equation into the density functional theory. As a result, the excited charge density is reiterated back into the Kohn-Sham equation, and the band structure is allowed to change dynamically. Even with the ground-state density functional, a larger demagnetization than RBA is found; after we expand Ortenzi's spin scaling method into an excited-state (laser) density functional, we find that the exchange splitting is indeed strongly reduced, as seen in the experiment. Both the majority and minority bands are shifted toward the Fermi level, but the majority shifts a lot more. The ultrafast reduction in exchange splitting occurs concomitantly with demagnetization. While our current theory is still unable to yield the same percentage loss in the spin moment as observed in the experiment, it predicts a correct trend that agrees with the experiments. With a better functional, we believe that our results can be further improved.

Intrinsic Delocalization during the Decay of Excitons in Polymeric Solar Cells.

In bulk heterojunction polymer solar cells, external photoexcitation results in localized excitons in the polymer chain. After hot exciton formation and subsequent relaxation, the dipole moment drives the electron to partially transfer to extended orbitals from the original localized ones, leading to self-delocalization. Based on the dynamic fluorescence spectra, the delocalization of excitons is revealed to be an intrinsic property dominated by exciton decay, acting as a bridge for the exciton to diffuse in the polymeric solar cell. The modification of the dipole moment enhances the efficiency of polymer solar cells.

Magnetic spin moment reduction in photoexcited ferromagnets through exchange interaction quenching: beyond the rigid band approximation.

The exchange interaction among electrons is one of the most fundamental quantum mechanical interactions in nature and underlies any magnetic phenomena from ferromagnetic ordering to magnetic storage. The current technology is built upon a thermal or magnetic field, but a frontier is emerging to directly control magnetism using ultrashort laser pulses. However, little is known about the fate of the exchange interaction. Here we report unambiguously that photoexcitation is capable of quenching the exchange interaction in all three 3d ferromagnetic metals. The entire process starts with a small number of photoexcited electrons which build up a new and self-destructive potential that collapses the system into a new state with a reduced exchange splitting. The spin moment reduction follows a Bloch-like law as M(z)(ΔE) = M(z)(0)(1 - ΔE/ΔE0)(1/ß), where ΔE is the absorbed photon energy and ß is a scaling exponent. A good agreement is found between the experimental and our theoretical results. Our findings may have a broader implication for dynamic electron correlation effects in laser-excited iron-based superconductors, iron borate, rare-earth orthoferrites, hematites and rare-earth transition metal alloys.

Absorption efficiency and heating kinetics of nanoparticles in the RF range for selective nanotherapy of cancer.

Radio-frequency (RF) waves have an excellent ability to penetrate into the human body, giving a great opportunity to activate/heat nanoparticles delivered inside the body as a contrast agent for diagnosis and treatment purposes. However the heating of nanoparticles in the RF range of the spectrum is controversial in the research community because of the low power load of RF waves and low absorption of nanoparticles in the RF range. This study uses a phenomenological approach to estimate the absorption efficiency of metal and dielectric nanoparticles in the RF range through a study of heating kinetics of those particles in radio wave field. We also discuss the specific features of heating kinetics of nanoparticles, such as a short time scale for heating and cooling of nanoparticles in a liquid biological environment, and the effect of the radiation field structure on the heating kinetics by single-pulse and multipulse RF radiation. FROM THE CLINICAL EDITOR: In this study a phenomenological approach was applied to estimate the absorption efficiency of radiofrequency radiation (RF) by metal and dielectric nanoparticles. Such nanoparticles can be designed and used for therapeutic purposes, like for localized heating and to activate nanoparticles by RF. The authors also discuss the differences in heating kinetics using single-pulse and multi-pulse RF radiation.

Deep localized distortion of alternating bonds and reduced transport of charged carriers in conjugated polymers under photoexcitation.

In a real bulk heterojunction polymer solar cell, after exciton separation in the heterojunction, the resulting negatively-charged carrier, a polaron, moves along the polymer chain of the acceptor, which is believed to be of significance for the charged carrier transport properties in a polymer solar cell. During the negative polaron transport, due to the external light field, the polaron, which is re-excited and induces deep localization, also forms a new local distortion of the alternating bonds. It is revealed that the excited polaron moves more slowly than the ground-state polaron. Furthermore, the velocity of the polaron moving along the polymer chain is crucially dependent on the photoexcitation. With an increase in the intensity of the optical field, the localization of the excited polaron will be deepened, with a decrease of the polaron's velocity. It is discovered that, for a charged carrier, photoexcitation is a significant factor in reducing the efficiency during the charged carrier transport in polymer solar cells. Mostly, the deep trapping effect of charged carrier in composite conjugated polymer solar cell presents an opportunity for the future application in nanoscale memory and imaging devices.

X-ray optics of gold nanoparticles.

Gold nanoparticles have been investigated as contrast agents for traditional x-ray medical procedures, utilizing the strong absorption characteristics of the nanoparticles to enhance the contrast of the detected x-ray image. Here we use the Kramers-Kronig relation for complex atomic scattering factors to find the real and imaginary parts of the index of refraction for the medium composed of single-element materials or compounds in the x-ray range of the spectrum. These complex index of refraction values are then plugged into a Lorenz-Mie theory to calculate the absorption efficiency of various size gold nanoparticles for photon energies in the 1-100 keV range. Since the output from most medical diagnostic x-ray devices follows a wide and filtered spectrum of photon energies, we introduce and compute the effective intensity-absorption-efficiency values for gold nanoparticles of radii varying from 5 to 50 nm, where we use the TASMIP model to integrate over all spectral energies generated by typical tungsten anode x-ray tubes with kilovolt potentials ranging from 50 to 150 kVp.

Photon statistics of resonance fluorescence in the limit of separated spectral lines.

We have studied the statistics of fluorescent photons emitted by a two-state atom in a laser beam in the limit where either the detuning or the Rabi frequency is large. For this case, the spectrum of resonance fluorescence has three separated lines. We have obtained closed form expressions for the conditional probability density for the emission of the nth photon and for the probability for emission of n photons in a time interval [0,T]. Our solutions are complementary to the known solutions for the case of perfect resonance.