Classical Energy Transfer Research Articles

Theory for ultrafast energy transfer in photosynthesis.

Photosynthesis has attracted much attention due to its extremely high energy transfer efficiency in the primary light capture stage. Numerical simulations based on energy transfer theory are helpful in exploring the physical mechanisms behind the dynamics of energy transfer. This article starts from the process of photosynthesis and explains the specific contents of two classical energy transfer theories, namely coherent and incoherent theories. Based on these theories, we discuss the numerical simulation methodology of perturbation approximation on the Fenna-Matthews-Olson (FMO) complex model. Finally, we compare the non-perturbation results with the perturbation results and further explore some energy transfer mechanisms. This work has the potential to stimulate ideas on attaining carbon neutrality through a more efficient photosynthesis process.

Modulating Resonance Energy Transfer with Supramolecular Control in a Layered Hybrid Perovskite and Chromium Photosensitizer Assembly.

Recently, the low-dimensional organic-inorganic halide perovskites (OIHP) have been exploited heavily for their favorable exciton dynamics, broad-band emission, remarkable stability, and tunable band-edge excited-state energy compared to their 3D counterparts for potential optoelectronic applications. Low-dimensional perovskites are generally good candidates for utilization as room-temperature photoluminescence (PL) materials. Further, doping divalent transition metals like Mn2+ into OIHP is expected to introduce a 4T1-6A1-based low-energy luminescence emission around 600 nm; an optical property that is favorable for biomedical optoelectronics. Doping Mn2+ in the perovskite lattice is also expected to induce the generation of cytotoxic singlet oxygen species (1O2), a ROS that is being exploited for various therapeutic applications. To integrate these optical and therapeutic properties of a 2D (PEA)2PbBr4 (Pb PeV; PEA = phenylethylammonium cation) perovskite alloyed with Mn2+ ions (Mn:PbPeV) and the option for a photoinduced energy transfer process involving a Cr(III)-based 1O2 generating photosensitizer (CrPS), we designed a unique purpose-built nanoassembly (Mn:PbPeV@PCD) using the encapsulation properties of a water-soluble polymer derived from β-cyclodextrin (PCD). Here the PCD is observed to modulate the classical internal energy transfer of Pb2+ exciton to alloyed Mn2+ orange emission, resulting in the emergence of a new blue emission. The addition of CrPS into the Mn:PbPeV@PCD to generate the CrPS@Mn:PbPeV@PCD assembly results in restoring perovskite luminescence followed by the external energy transfer to CrPS. We have elucidated the mechanism of these cascade energy transfer processes between multiple components using steady-state and time-resolved luminescence techniques. Efficient ROS generation and its potential to induce an oxidation reaction of a biomolecule are realized using guanine as the target molecule. Further photoinduced cleavage studies with biomolecules confirmed the efficacy of the nanoassembly in inducing the cleavage of guanine-rich DNA. The study opens up a new direction in the field of perovskite for biomedical applications.

Damköhler number scaling of active cascade effects in turbulent premixed combustion

Effects of combustion heat release on turbulent velocity and scalar statistics are investigated as a function of the Damköhler number using three direct numerical simulation databases of spatially developing turbulent premixed jet flames. At low Karlovitz numbers, where heat-release effects dominate turbulent kinetic energy budgets, their relative significance scales with the integral Damköhler number in a priori Reynolds-Averaged Navier–Stokes (RANS) statistics and the filter Damköhler number in Large Eddy Simulation (LES). The Damköhler-number scaling of counter-gradient transport in this regime follows theoretical arguments underpinning linear-algebraic turbulence models, which explains their efficacy at low Karlovitz numbers. Conversely, at moderate Karlovitz numbers, LES subfilter turbulence is more strongly influenced by heat-release effects than the analogous large-scale RANS turbulence. This is consistent with the notion of an “active cascade,” which postulates that heat-release-induced volumetric expansion competes on intermediate scales with classical forward-cascade energy transfer. LES exposes these dynamics as dominant subfilter-scale physics, unlike in RANS, where they are secondary to the effects of mean-shear production at the large scales. The significance of subfilter-scale interactions is promoted by the LES filter itself, which modifies the RANS spectral basis by incorporating local flame-normal averaging. This is highlighted by comparing LES fields obtained using a 3D filter to those using a modified 2D filter, excluding the flame-normal direction, which significantly reduces the apparent influence of heat-release effects but is not representative of LES in practice. The subfilter modeling challenges posed by these distinctions at moderate Karlovitz numbers and order-unity Damköhler numbers remain to be understood.

A novel photochromic ceramics with reversible luminescence modulation and light bleaching behavior: Sm3+-doped KSr2Nb5O15

A novel tetragonal tungsten bronze (TTB) type Sm3+-doped KSr2Nb5O15 (KSN-Sm) optical ceramic is fabricated by atmosphere sintering technology. A reversible photochromic effect between faint yellow and olive colors and accompanied luminescence modulation behaviour can be realized by alternating the 395 nm light irradiation and thermal treatment. The thermal stimulus model is introduced to modify the classical resonance energy transfer mechanism. The results show that the optimal luminescence modulation ratio △Rt about the red emission (601 nm) intensity amounted to 60.0 %, and the KSN-Sm ceramic exhibits excellent luminescence modulation rate and reproducibility. The colored KSN-Sm ceramic can be partly bleached by external light stimulus (620 nm), and the luminescence emission intensity can be recovered from 45 % to 84.2 %. The light bleaching efficiency is strongly dependent on the irradiation wavelength, exposure duration and irradiation dose. These discoveries pave the way to develop new luminescence materials with TTB structure.

Plasmon-induced photoluminescence and Raman enhancement in Pr:CaF2 crystal by embedded silver nanoparticles

Photoluminescence (PL) enhancement of rare earth ions is in high demand due to their crucial applications in optoelectronics devices and biomedical frequency up-convertors for endoscopy, which could be realized by a plasmonic field enhancement effect of metallic nanoparticles (NPs). In this work, both the PL emission and Raman scattering enhancement of Pr3+ ions in CaF2 crystal host have been observed for the first time by embedding silver NPs. By Ag+ ion implantation, Ag NPs (around 5 nm) have been encapsulated into the Pr:CaF2 matrix. Analysis of the difference between linear optical absorption and PL excitation spectra within the plasmon band, the mechanism of observed PL enhancement has been attributed to the local field enhancement induced by the plasmonic NPs. The classical energy transfer process nanoparticle-emitter was not present. The detailed analysis of the PL enhancement induced by unannealed and annealed Ag NPs is compared under the measurement of PL decay, showing the dominant mechanism of the increased absorption and radiative decay rate, respectively. This work shows an efficient method to enhance PL emission of rare earth ions in the crystal based on the embedded metallic NPs, which could be used to optimize the photonic sensors and light emitting devices.

Photophysical properties of porphyrinic covalent cages endowed with different flexible linkers

In-depth photophysical studies of four flexible covalent cages bearing either two free-base porphyrins or one free-base porphyrin and one Zn(II) porphyrin, connected by linkers of different lengths, are reported. In the case of the cages with two free-base porphyrins, exciton coupling between the porphyrins is evidenced by large and split Soret bands in the absorption spectra, but the different length of the linkers has only a slight effect on their emission properties. Strong electronic interactions between the porphyrins are also evidenced for the cages that incorporate a free-base porphyrin and a Zn(II) porphyrin, with a more pronounced splitting of the Soret band for the system with longer linkers. In these cages, following excitation of the Zn-porphyrin component, an almost quantitative energy transfer to the free-base unit occurs, with a rate 1.4 times faster in the cage with longer linkers (1.4 × 10[Formula: see text] s[Formula: see text] vs. 1.0 × 10[Formula: see text] s[Formula: see text]. This difference might reflect the more flattened conformation adopted by the cage equipped with longer and more flexible linkers, the latter allowing for a shorter interplanar distance between the porphyrins. The results are discussed in terms of classical and short-range energy transfer mechanisms.

Analysis of the classical phase space and energy transfer for two rotating dipoles with and without external electric field.

We explore the classical dynamics of two interacting rotating dipoles that are fixed in the space and exposed to an external homogeneous electric field. Kinetic energy transfer mechanisms between the dipoles are investigated by varying both the amount of initial excess kinetic energy of one of them and the strength of the electric field. In the field-free case, and depending on the initial excess energy, an abrupt transition between equipartition and nonequipartition regimes is encountered. The study of the phase space structure of the system as well as the formulation of the Hamiltonian in an appropriate coordinate frame provide a thorough understanding of this sharp transition. When the electric field is turned on, the kinetic energy transfer mechanism is significantly more complex and the system goes through different regimes of equipartition and nonequipartition of the energy including chaotic behavior.

Control of plasmon emission and dynamics at the transition from classical to quantum coupling.

With nanosecond radiative lifetimes, quenching dominates over enhancement for conventional fluorescence emitters near metal interfaces. We explore the fundamentally distinct behavior of photoluminescence (PL) with few-femtosecond radiative lifetimes of a coupled plasmonic emitter. Controlling the emitter-surface distance with subnanometer precision by combining atomic force and scanning tunneling distance control, we explore the unique behavior of plasmon dynamics at the transition from long-range classical resonant energy transfer to quantum coupling. Because of the ultrafast radiative plasmon emission, classical quenching is completely suppressed. Field-enhanced behavior dominates until the onset of quantum coupling dramatically reduces emission intensity and field enhancement, as verified in concomitant tip-enhanced Raman measurements. The entire distance behavior from tens of nanometers to subnanometers can be described using a phenomenological rate equation model and highlights the new degrees of freedom in radiation control enabled by an ultrafast radiative emitter near surfaces.

Effect of temperature on optical spectra and relaxation dynamics of Sm3+ in Gd3Ga5O12 single crystals

Single crystals of Gd3Ga5O12 (GGG) doped with 2 at.% and 10 at.% of Sm3+ were fabricated by the Czochralski method. Optical absorption and emission spectra as well as luminescence decay curves for these crystals were recorded at different temperatures ranging from 5 K to 300 K. The energies of the crystal field sublevels of selected multiplets were determined based on optical spectra recorded at T = 5 K. It has been found that widths of spectral lines related to transitions between individual crystal field levels of multiplets involved increase by factors of 5–7 when the sample temperature grows from 5 K to 300 K. In contrast to this the positions of spectral lines appear to be independent of temperature. Temperature dependence of the 4G5/2 luminescence lifetime was determined for both concentrations of samarium. Luminescence decay curves follow a single-exponential time dependence when Sm3+ concentration amounts to 2 at.% but a non-exponential decay kinetic and efficient quenching process were observed in highly-doped sample. The Inokuti–Hirayama classical energy transfer model was utilized successfully to account for time dependence of an experimental decay curves recorded for GGG:10 at.% Sm crystal.

Classical analog of quasilinear Landau-Zener tunneling

In this paper we develop an analytical framework to study the effect of nonlinearity on irreversible energy transfer in a system of two weakly coupled oscillators with time-dependent parameters, with special attention to an analogy between classical energy transfer and nonadiabatic quantum tunneling. For preciseness, we suppose that a linear oscillator with constant parameters is excited by an initial impulse but a coupled quasilinear oscillator with slowly varying parameters is initially at rest. It is shown that the equations of the slow passage through resonance in this system are identical to quasilinear equations of nonadiabatic Landau-Zener tunneling. Due to revealed equivalence, a recently found analogy between irreversible energy transfer in a classical linear system and conventional linear Landau-Zener tunneling can be extended to quasilinear systems. An explicit analytical solution of the quasilinear problem is found with the help of an iteration procedure, wherein the linear solution is chosen as an initial approximation. Correctness of the constructed approximations is confirmed by numerical simulations. The results presented in this paper, in addition to providing an analytical framework for understanding the transient dynamics of coupled oscillators, suggest an approximate procedure for solving the quasilinear Landau-Zener equations with arbitrary initial conditions over a finite time interval.

The Grover energy transfer algorithm for relativistic speeds

Grover's algorithm for quantum search can also be applied to classical energy transfer. The procedure takes a system in which the total energy is equally distributed among N subsystems and transfers most of it to one marked subsystem. We show that in a relativistic setting the efficiency of this procedure can be improved. We will consider the transfer of relativistic kinetic energy in a series of elastic collisions. In this case, the number of steps of the energy transfer procedure approaches 1 as the initial velocities of the objects become closer to the speed of light. This is a consequence of introducing nonlinearities in the procedure. However, the maximum attainable transfer will depend on the particular combination of speed and number of objects. In the procedure, we will use N elements, as in the classical non-relativistic case, instead of the log2(N) states of the quantum algorithm.

Motional effects on the efficiency of excitation transfer

Energy transfer plays a vital role in many natural and technological processes. In this work, we study the effects of mechanical motion on the excitation transfer through a chain of interacting molecules with applications to biological scenarios of transfer processes. Our investigation demonstrates that, for various types of mechanical oscillations, the transfer efficiency is significantly enhanced over that of comparable static configurations. This enhancement is a genuine quantum signature and requires the collaborative interplay between the quantum-coherent evolution of the excitation and the mechanical motion of the molecules; it has no analogue in the classical incoherent energy transfer. This effect may not only occur naturally but also be exploited in artificially designed systems to optimize transport processes. As an application, we discuss a simple and hence robust control technique.

Plasmonic Enhancement or Energy Transfer? On the Luminescence of Gold‐, Silver‐, and Lanthanide‐Doped Silicate Glasses and Its Potential for Light‐Emitting Devices

AbstractWith the technique of synchrotron X‐ray activation, molecule‐like, non‐plasmonic gold and silver particles in soda‐lime silicate glasses can be generated. The luminescence energy transfer between these species and lanthanide(III) ions is studied. As a result, a significant lanthanide luminescence enhancement by a factor of up to 250 under non‐resonant UV excitation is observed. The absence of a distinct gold and silver plasmon resonance absorption, respectively, the missing nanoparticle signals in previous SAXS and TEM experiments, the unaltered luminescence lifetime of the lanthanide ions compared to the non‐enhanced case, and an excitation maximum at 300–350 nm (equivalent to the absorption range of small noble metal particles) indicate unambiguously that the observed enhancement is due to a classical energy transfer between small noble metal particles and lanthanide ions, and not to a plasmonic field enhancement effect. It is proposed that very small, molecule‐like noble metal particles (such as dimers, trimers, and tetramers) first absorb the excitation light, undergo a singlet‐triplet intersystem crossing, and finally transfer the energy to an excited multiplet state of adjacent lanthanide(III) ions. X‐ray lithographic microstructuring and excitation with a commercial UV LED show the potential of the activated glass samples as bright light‐emitting devices with tunable emission colors.

Metal-Induced Photoluminescence Quenching of Organic Molecular Crystals

We present a detailed study of the thickness dependence of the photoluminescence of ultrathin organic films on Au(111). For the evaluation of the observed intensities a new differential analysis method is introduced. The obtained quantum yield indicates a complete quenching in the thickness range below 4 monolayers (ML) for the two crystal polymorphs and saturates above 12 ML. Several models of energy transfer were applied to our data. We conclude that only consideration of both exciton diffusion and dissociation at the organic−metal interface in combination with classical energy transfer results in a complete and satisfactory description.

Analysis of close proximity quenching of phosphorescent metalloporphyrin labels in oligonucleotide structures

Quenching of phosphorescent platinum(II) and palladium(II) coproporphyrin (MeCP) labelled oligonucleotides was investigated. Strong hybridization-specific quenching was observed in duplex DNA structures with a variety of quenchers and with two identical porphyrin labels when in close proximity. Classical resonance energy transfer mechanism was ruled out, since quenching did not correlate with spectral overlaps and lifetime changes were insignificant. Quenching of MeCP by the free quenchers in solution revealed that porphyrin–porphyrin quenching is predominantly static while other dyes quench dynamically. The results suggest that the quenching in DNA duplex proceeds via direct contact.

Experimental study of the dynamics of neutron emission from the GOL-3 multimirror trap

In experiments on the plasma heating and confinement in the GOL-3 multimirror trap, a deuterium plasma with a density of ∼1015 cm−3 and an ion temperature of 1–2 keV is confined for more than 1 ms. The plasma is heated by a relativistic electron beam. The ion temperature, which was measured by independent methods, reached 1.5–2 keV after the beginning of the beam injection. Since such a fast ion heating cannot be explained by the classical energy transfer from electrons to ions through binary collisions, a theoretical model of collective energy transfer was proposed. In order to verify this model, a new diagnostics was designed to study the dynamics of neutron emission from an individual mirror cell of the multimirror trap during electron beam injection. Intense neutron bursts predicted by this model were detected experimentally. Periodic neutron flux modulation caused by the macroscopic plasma flow along the solenoid was observed. The revealed mechanism of fast ion heating can be used to achieve fusion temperatures in the multimirror trap.

Er-defect complexes and isolated Er center spectroscopy in Er-implanted GaN

Photoluminescence (PL), photoluminescence excitation (PLE) spectra and luminescence decay of the Er 3+ 4 I 13/2→ 4 I 15/2 transition are investigated at 7 K in Er-implanted GaN samples. Under below-gap excitation, PL and PLE spectra reveal the existence of two types of Er centers. One type of Er center which can only be excited by resonant intra 4f shell transition is predominant while other Er centers are clearly excited via local defects. Evolution of Er luminescence as a function of implantation dose and implantation geometry is presented for both types of Er centers. Luminescence dynamics study shows that the 4 I 13/2 manifold has a shorter lifetime ( τ∼1 ms) when Er ions are part of Er-defect complexes than when Er ions are isolated from any defect ( τ=3.8 ms). This result indicates the existence of non-radiative energy transfers in Er-defect complexes from Er ions towards defects or impurities. Er decay in Er-defect complexes is then successfully compared with classical energy transfer models.

Semiclassical modeling of state-specific dissociation rates in diatomic gases

A nonempirical, containing no adjustable parameters, theoretical model is suggested for calculations of state-specific dissociation rates in diatomic gases. Effects of molecular rotation and three dimensionality of collisions are consistently accounted for. The model is based upon a modified forced harmonic oscillator (FHO) scaling, with anharmonic frequency correction and energy symmetrization. The FHO scaling allows close-coupled calculations of multiquantum transitions between vibrational states, and it requires evaluation of collisional energy transfer to classical oscillator. Three-dimensional classical energy transfer models in both free-rotation and impulsive (sudden) approximations were used in conjunction with the FHO quantum scaling. The new theory describes the role of various degrees of freedom in dissociation both qualitatively and quantitatively. One of the predictions is that at low and moderate temperatures, dissociation is strongly preferential, with state-specific rates sharply increasing with vibrational energy; however, at high temperatures, the rate dependence on vibrational energy becomes less steep, turning into a virtually nonpreferential. Calculated thermal (equilibrium) and nonequilibrium dissociation rates of oxygen and nitrogen show a very good agreement with shock-tube experimental data taken from the literature.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger–Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8×3.4×1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially.

Collision-induced activation of the β-hydride elimination reaction of isobutyl iodide dissociatively chemisorbed on Al(111)

The collision-induced activation of the endothermic surface reaction of isobutyl iodide chemisorbed on an Al(111) surface is demonstrated using inert-gas, hyperthermal atomic beams. The collision-induced reaction (CIR) is highly selective towards promoting the β-hydride elimination pathway of the chemisorbed isobutyl fragments. The cross section for the collision-induced reaction was measured over a wide range of energies (14–92 kcal/mol) at normal incidence for Ar, Kr, and Xe atom beams. The CIR cross section exhibits scaling as a function of the normal kinetic energy of the incident atoms. The threshold energy for the β-hydride elimination reaction calculated from the experimental results using a classical energy transfer model is ∼1.1 eV (∼25 kcal/mol). This value is in excellent agreement with that obtained from an analysis of the thermally activated kinetics of the reaction. The measured cross section shows a complex dependence on both the incident energy of the colliding atom and the thermal energy provided by the surface where the two energy modes are interchangeable. The dynamics are explained on the basis of an impulsive, bimolecular collision event where the β-hydride elimination proceeds via a possible tunneling mechanism. The threshold energy calculated in this manner is an upper limit given that it is derived from an analysis which ignores excitations of the internal modes of the chemisorbed alkyl groups.