Impulsive Photoexcitation Research Articles

Exciton Diffusion and Annihilation in an sp2 Carbon-Conjugated Covalent Organic Framework.

To optimize the optical and optoelectronic functionalities of two-dimensional (2D) covalent organic frameworks (COFs), detailed properties of emissive and nonradiative pathways after photoexcitation need to be elucidated and linked to particular structural designs. Here, we use transient absorption (TA) spectroscopy to study the colloidal suspension of the full sp2 carbon-conjugated sp2c-COF and characterize the spatial extent and diffusion dynamics of the emissive excitons generated by impulsive photoexcitation. The ∼3.5 Å stacking distance between 2D layers results in cofacial pyrene excitons that diffuse through the framework, while the state that dominates the emissive spectrum of the polycrystalline solid is assigned to an extended cofacial exciton whose 2D delocalization is promoted by C═C linkages. The subnanosecond kinetics of a photoinduced absorption (PIA) signal in the near-infrared, attributed to a charge-separated exciton, or polaron pair, reflects three-dimensional (3D) exciton diffusion as well as long-range exciton-exciton annihilation driven by resonance interactions. Within our experimental regime, doubling the excitation intensity results in a 10-fold increase in the estimated exciton diffusion length, from ∼3 to ∼30 nm, suggesting that higher lattice temperature may enhance exciton mobility in the COF colloid.

Photoinduced Charge Transfer Dynamics in the Carotenoid-Porphyrin-C60 Triad via the Linearized Semiclassical Nonequilibrium Fermi's Golden Rule.

The nonequilibrium Fermi's golden rule (NE-FGR) describes the time-dependent rate coefficient for electronic transitions when the nuclear degrees of freedom start out in a nonequilibrium state. In this paper, the linearized semiclassical (LSC) approximation of the NE-FGR is used to calculate the photoinduced charge transfer (CT) rates in the carotenoid-porphyrin-C60 molecular triad dissolved in explicit tetrahydrofuran. The initial nonequilibrium state corresponds to impulsive photoexcitation from the equilibrated ground state to the ππ* state, and the porphyrin-to-C60 and carotenoid-to-C60 CT rates are calculated. Our results show that accounting for the nonequilibrium nature of the initial state significantly enhances the transition rate of the porphyrin-to-C60 CT process. We also derive the instantaneous Marcus theory (IMT) from LSC NE-FGR, which casts the CT rate coefficients in terms of a Marcus-like expression, with explicitly time-dependent reorganization energy and reaction free energy. IMT is found to reproduce the CT rates in the system under consideration remarkably well.

Phase control of coherent acoustic phonons in gold bipyramids for optical memory and manipulating plasmon–exciton coupling

Recent efforts have targeted manipulation of nanomaterial vibrational modes in applications such as chemical/mass sensing, optical switching, and phonon-driven photochemistry. While impulsive photoexcitation can generate coherent phonons, multiple excitation pulses offer the prospect of control and manipulation of coherent phonon modes for functions of optical memory and logic. Here, we use such an approach to inject an arbitrary coherent phonon phase into a colloidal ensemble of highly monodisperse gold bipyramids. We then demonstrate that this technique can be applied to a system that exhibits plasmon–exciton coupling to further manipulate the hybridization of the system. This ability to manipulate acoustic phonons and hybridization can enable optical logic applications of acoustic phonons in addition to optical memory.

Ultrafast carrier recombination in highly n-doped Ge-on-Si films

We study the femtosecond carrier dynamics of n-type doped and biaxially strained Ge-on-Si films which occurs upon impulsive photoexcitation by means of broadband near-IR transient absorption spectroscopy. The modeling of the experimental data takes into account the static donor density in a modified rate equation for the description of the temporal recombination dynamics. The measurements confirm the negligible contribution at a high n-type doping concentration, in the 1019 cm−3 range, of Auger processes as compared to defect-related Shockley-Read-Hall recombination. Energy resolved dynamics reveal further insights into the doping-related band structure changes and suggest a reshaping of direct and indirect conduction band valleys to a single effective valley along with a significant spectral broadening of the optical transitions.

Fano resonance between coherent acoustic phonon oscillations and electronic states near the bandgap of photoexcited GaAs

Impulsive photo-excitation of solids results in a travelling strain pulse which manifests itself as coherent acoustic phonon oscillations. These oscillations have been extensively studied using time-resolved pump-probe spectroscopy. In the present work, we report the generation of extremely long-lived, coherent longitudinal acoustic phonon oscillations in intrinsic GaAs (100), with clear and unambiguous evidence of Fano interference between these oscillations and the continuum of electronic states close to the bandgap. Fano resonance is a widespread phenomenon observed in atomic systems and condensed media that arises from quantum interference between a continuum of quantum states and a discrete quantum state. Among other techniques, Fano resonance has been investigated with respect to optical phonons studied with Raman Spectroscopy. In the present work, we investigate Fano resonance in coherent phonon oscillations generated without the aid of any capping layer, dopants or substrate/interface effects. Since Fano resonance is sensitive to changes in electronic structure, doping and defects, these observations are important to the field of picosecond ultrasonics which is used for non-destructive depth profiling of solids and for carrier diffusion studies.

Temperature Independence of Ultrafast Photoisomerization in Thermophilic Rhodopsin: Assessment versus Other Microbial Proton Pumps.

Primary photochemical events in the unusually thermostable proton pumping rhodopsin of Thermus thermophilus bacterium (TR) are reported for the first time. Internal conversion in this protein is shown to be significantly faster than in bacteriorhodopsin (BR), making it the most rapidly isomerizing microbial proton pump known. Internal conversion (IC) dynamics of TR and BR were recorded from room temperature to the verge of thermal denaturation at 70 °C and found to be totally independent of temperature in this range. This included the well documented multiexponential nature of IC in BR, suggesting that assignment of this to ground state structural inhomogeneity needs revision. TR photodynamics were also compared with that of the phylogenetically more similar proton pump Gloeobacter rhodopsin (GR). Despite this similarity GR has poor thermal stability, and the excited state decays significantly more slowly and exhibits very prominent stretched exponential behavior. Coherent torsional wave-packets induced by impulsive photoexcitation of TR and GR show marked resemblance to each other in frequency and amplitude and differ strikingly from similar signatures in pump-probe data of BR and other microbial retinal proteins. Possible correlations between IC rates and thermal stability and the promise of using torsional coherence signatures for understanding chromophore protein binding in microbial retinal proteins are discussed.

Dynamic separation of electron excitation and lattice heating during the photoinduced melting of the periodic lattice distortion in 2H-TaSe2

The photoinduced structural dynamics in 2H-TaSe2 in the charge-density wave (CDW) state is investigated using MeV ultrafast electron diffraction. By simultaneously tracking both the melting of the periodic lattice distortion (PLD) associated with the CDW and the lattice heating, following an impulsive photoexcitation, the separate contributions of electronic excitation and lattice thermalization to the melting process are disentangled in the time domain. Two distinct time-constants, reflecting the corresponding individual dynamics of the subsystems, are observed. Our experimental results demonstrate that the PLD in 2H-TaSe2 is first suppressed promptly by the electronic excitation and scattering, and then subsequently by lattice thermalization through electron-phonon interaction, on a much longer time scale. This latter leads to the final, full melting of the PLD.

Ultrafast Charge Separation in Low Band-Gap Polymer Blend for Photovoltaics

We track ultrafast charge dissociation in a particularly promising low-band-gap- polymer:fullerene blend for organic photovoltaics. Impulsive photoexcitation with excess energy leads to a 30-fs formation of an hot charge transfer state, precursor of free carriers.

HEMT-BASED NANOMETER DEVICES TOWARD TERAHERTZ ERA

The terahertz region is one of the unexplored bands. This paper first reviews the present status of conventional high-speed devices, especially InP-based high electron mobility transistors (HEMTs), and addresses the technological problems facing the goal of terahertz operation. As an alternative approach to solve these problems, we developed a plasmon-resonant photomixer for realizing a coherent terahertz continuous-wave source. Preliminary results on electromagnetic response to impulsive photoexcitation at room temperature are reported briefly.

Comparing photoinduced vibrational coherences in bacteriorhodopsin and in native and locked retinal protonated Schiff bases

Low frequency excited state vibrational coherences induced by impulsive photoexcitation in bacteriorhodopsin are detected via femtosecond pump–probe spectroscopy, and compared with similar data in retinal protonated Schiff bases of native and locked retinals. At delays above ∼100 fs a single vibration below 200 fs dominates the detected spectral modulations. Its frequency of ∼120 in retinal protonated Schiff base is virtually unchanged by locking the C 13C 14 bond in the trans or cis configurations, but is increased to 170 cm −1 within the protein environment. The implications of this result on the part played by the protein in directing the reactivity of the retinal within bacteriorhodopsin is discussed.

Modulation of the bonding-antibonding splitting in Te by coherent phonons

We present femtosecond time-resolved measurements of the dielectric tensor of tellurium following intense photoexcitation. Strong impulsive photoexcitation of crystalline tellurium weakens the covalent bonds between atoms, which undergo coherent oscillations (at $>3$ THz) as they relax to new equilibrium positions. As this photoexcitation drives the lattice toward a band-crossing transition, we track the decrease and oscillation of the bonding-antibonding splitting. The reduction of the bonding-antibonding splitting exceeds the band gap for 100 fs, indicating a transient state with crossed bands.

Coherent dynamics of photoexcited green fluorescent proteins.

The coherent dynamics of vibronic wave packets in the green fluorescent protein is reported. At room temperature the nonstationary dynamics following impulsive photoexcitation displays an oscillating optical transmissivity pattern with components at 67 fs (497 cm(-1)) and 59 fs (593 cm(-1)). Our results are complemented by ab initio calculations of the vibrational spectrum of the chromophore. This analysis shows the interplay between the dynamics of the aminoacidic structure and the electronic excitation in the primary optical events of green fluorescent proteins.

Impulsive excitation of coherent vibrational motion ground surface dynamics induced by intense short pulses

A framework for understanding impulsively photoinduced vibrational coherent motion on the ground electronic surface is presented. In particular strong resonant excitation to a directly dissociative electronic surface is considered. Three distinct approaches are employed. A two surface Fourier wavepacket method explicitly including the field explores this process in isolated molecules. A coordinate dependent two-level system is employed to develop a novel analytical approximation to the photoinduced quantum dynamics. The negligible computational requirements make it a powerful interactive tool for reconstructing the impulsive photoexcitation stage. Its analytical nature provides closed form expressions for the photoinduced changes in the material. Finally the full simulation of the process including the solvent effects is carried out by a numerical propagation of the density operator. In all three techniques the excitation field is treated to all orders, allowing an analysis of current experiments using strong fields, resulting in substantial photoconversion. The emerging picture is that the impulsive excitation carves a coherent dynamical ‘‘hole’’ out of the ground surface density. A rigorous definition of the dynamical ‘‘hole’’ is constructed and used to define a measure of its coherence. In particular all photoinduced time dependence in the system can be directly related to the dynamical ‘‘hole.’’ All three techniques are used to simulate the pump probe experiment on the symmetric stretch mode of I3−, including electronic and vibrational dephasing.