Ps Time Scale Research Articles

Dynamical matrix propagator scheme for large-scale proton dynamics simulations.

We derive a matrix formalism for the simulation of long range proton dynamics for extended systems and timescales. On the basis of an ab initio molecular dynamics simulation, we construct a Markov chain, which allows us to store the entire proton dynamics in an M × M transition matrix (where M is the number of oxygen atoms). In this article, we start from common topology features of the hydrogen bond network of good proton conductors and utilize them as constituent constraints of our dynamic model. We present a thorough mathematical derivation of our approach and verify its uniqueness and correct asymptotic behavior. We propagate the proton distribution by means of transition matrices, which contain kinetic data from both ultra-short (sub-ps) and intermediate (ps) timescales. This concept allows us to keep the most relevant features from the microscopic level while effectively reaching larger time and length scales. We demonstrate the applicability of the transition matrices for the description of proton conduction trends in proton exchange membrane materials.

Efficient Plasmon-Mediated Energy Funneling to the Surface of Au@Pt Core-Shell Nanocrystals.

The structure and ultrafast photodynamics of ∼8 nm Au@Pt core-shell nanocrystals with ultrathin (<3 atomic layers) Pt-Au alloy shells are investigated to show that they meet the design principles for efficient bimetallic plasmonic photocatalysis. Photoelectron spectra recorded at two different photon energies are used to determine the radial concentration profile of the Pt-Au shell and the electron density near the Fermi energy, which play a key role in plasmon damping and electronic and thermal conductivity. Transient absorption measurements track the flow of energy from the plasmonic core to the electronic manifold of the Pt shell and back to the lattice of the core in the form of heat. We show that strong coupling to the high density of Pt(d) electrons at the Fermi level leads to accelerated dephasing of the Au plasmon on the femtosecond time scale, electron-electron energy transfer from Au(sp) core electrons to Pt(d) shell electrons on the sub-picosecond time scale, and enhanced thermal resistance on the 50 ps time scale. Electron-electron scattering efficiently funnels hot carriers into the ultrathin catalytically active shell at the nanocrystal surface, making them available to drive chemical reactions before losing energy to the lattice via electron-phonon scattering on the 2 ps time scale. The combination of strong broadband light absorption, enhanced electromagnetic fields at the catalytic metal sites, and efficient delivery of hot carriers to the catalyst surface makes core-shell nanocrystals with plasmonic metal cores and ultrathin catalytic metal shells promising nanostructures for the realization of high-efficiency plasmonic catalysts.

Photoswitching mechanism of a fluorescent protein revealed by time-resolved crystallography and transient absorption spectroscopy

Reversibly switchable fluorescent proteins (RSFPs) serve as markers in advanced fluorescence imaging. Photoswitching from a non-fluorescent off-state to a fluorescent on-state involves trans-to-cis chromophore isomerization and proton transfer. Whereas excited-state events on the ps timescale have been structurally characterized, conformational changes on slower timescales remain elusive. Here we describe the off-to-on photoswitching mechanism in the RSFP rsEGFP2 by using a combination of time-resolved serial crystallography at an X-ray free-electron laser and ns-resolved pump–probe UV-visible spectroscopy. Ten ns after photoexcitation, the crystal structure features a chromophore that isomerized from trans to cis but the surrounding pocket features conformational differences compared to the final on-state. Spectroscopy identifies the chromophore in this ground-state photo-intermediate as being protonated. Deprotonation then occurs on the μs timescale and correlates with a conformational change of the conserved neighbouring histidine. Together with a previous excited-state study, our data allow establishing a detailed mechanism of off-to-on photoswitching in rsEGFP2.

Structural and dynamical characterization of the S4 state of the Kok-Joliot’s cycle by means of QM/MM Molecular Dynamics Simulations

Water oxidation occurring in oxygenic natural photosynthesis is catalyzed by the protein-cofactor complex Photosystem II. The catalytic cycle leading to the water splitting into protons, electrons and molecular oxygen, consists of five consecutive steps, namely S0-S4. Here, using QM/MM Molecular Dynamics simulations, we characterized structural and magnetic properties of the putative S4 state prior to O2 release, considering two different spin multiplicities. Our results show an overall stability for both simulated systems in the ps timescale. Nonetheless, analysis of structural and magnetic properties identified discrepancies between the two simulations, conceivably having different consequences on the O2 evolution.

Pivotal role of the redox-active tyrosine in driving the water splitting catalyzed by photosystem II.

Photosynthetic water oxidation is catalyzed by the Mn4Ca cluster in photosystem II (PSII). The nearby redox-active tyrosine (YZ) serves as a direct electron acceptor of the Mn4Ca cluster and it forms a low-barrier H-bond (LBHB) with a neighboring histidine residue (D1-His190). Experimental evidence indicates that YZ oxidation triggers changes in the hydrogen bonding network that precede proton abstraction from the Mn4Ca cluster. In order to characterize such changes, we compare ab initio molecular dynamics simulations of different states of the catalytic cycle of PSII with dynamics of isolated tyrosine models (namely, p-cresol) in different oxidation states. The systematic comparison of the H-bond networks in different simulated systems suggests that the YZ oxidation leads to a water hydration pattern which is more similar to that of the neutral p-cresol rather than that of the p-cresol anion. Our simulations also reveal the twofold nature of the interactions between YZ and the Mn4Ca cluster. Firstly, the YZ oxidation triggers rapid structural changes of the H-bond pattern in the proximity of the cluster which have been observed to propagate on the ps time scale on the Ca2+ hydration shell up to other water molecules in the proximity of the cluster. Secondly, it is clear that YZ interacts with the Mn4Ca cluster also through Coulombic interactions mediated by CP43-Arg357 through the remaining positive charge of the pair. Our results are able to identify, for the first time, the structural rearrangements guided by the oxidation of YZ necessary for the evolution of the water splitting reaction in PSII. Based on these findings, we propose a mechanism of structural changes which is functional towards the progression of the catalytic cycle in PSII.

Evidence for ultrafast formation of tribenzoylgermyl radicals originating from tetraacylgermane photoinitiators

We report strong evidence for the ultrafast formation of tribenzoylgermyl radicals originating from tetraacylgermane photoinitiators on a ps-time scale. In comparison to previous studies, the result can be related to a high initiation efficiency.

Ultrafast spectroscopy of biliverdin dimethyl ester in solution: pathways of excited-state depopulation.

Biliverdin is a bile pigment that has a very low fluorescence quantum yield in solution, but serves as a chromophore in far-red fluorescent proteins being developed for bio-imaging. In this work, excited-state dynamics of biliverdin dimethyl ether (BVE) in solvents were investigated using femtosecond (fs) and picosecond (ps) time-resolved absorption and fluorescence spectroscopy. This study is the first fs timescale investigation of BVE in solvents, and therefore revealed numerous dynamics that were not resolved in previous, 200 ps time resolution measurements. Viscosity- and isotope-dependent experiments were performed to identify the contributions of isomerization and proton transfer to the excited-state dynamics. In aprotic solvents, a ∼2 ps non-radiative decay accounts for 95% of the excited-state population loss. In addition, a minor ∼30 ps emissive decay pathway is likely associated with an incomplete isomerization process around the C15[double bond, length as m-dash]C16 double bond that results in a flip of the D-ring. In protic solvents, the dynamics are more complex due to hydrogen bond interactions between solute and solvent. In this case, the ∼2 ps decay pathway is a minor channel (15%), whereas ∼70% of the excited-state population decays through an 800 fs emissive pathway. The ∼30 ps timescale associated with isomerization is also observed in protic solvents. The most significant difference in protic solvents is the presence of a >300 ps timescale in which BVE can decay through an emissive state, in parallel with excited-state proton transfer to the solvent. Interestingly, a small fraction of a luminous species, which we designate lumin-BVE (LBVE), is present in protic solvents.

Molecular origins of bulk viscosity in liquid water.

The rapid equilibrium fluctuations of water molecules are intimately connected to the rheological response; molecular motions resetting the local structure and stresses seen as flow and volume changes. In the case of water or hydrogen bonding liquids generally, the relationship is a non-trivial consideration due to strong directional interactions complicating theoretical models and necessitating clear observation of the timescale and nautre of the associated equilibrium motions. Recent work has illustrated a coincidence of timescales for short range sub-picosecond motions and the implied timescale for the shear viscosity response in liquid water. Here, neutron and light scattering methods are used to experimentally illustrate the timescale of bulk viscosity and provide a description of the associated molecular relaxation. Brillouin scattering has been used to establish the timescale of bulk viscosity; and borrowing the Maxwell approach, the ratio of the bulk viscosity, ζ, to the bulk modulus, K, yields a relaxation time, τB, which emerges on the order of 1-2 ps in the 280 K to 303 K temperature range. Inelastic neutron scattering is subsequently used to describe the motions of water and heavy water at the molecular scale, providing both coherent and incoherent scattering data. A rotational (alternatively described as localized) motion of water protons on the 1-2 ps timescale is apparent in the incoherent scattering spectra of water, while the coherent spectra from D2O on the length scale of the first sharp diffraction peak, describing the microscopic density fluctuations of water, confirms the relaxation of water structure at a comparable timescale of 1-2 ps. The coincidence of these three timescales provides a mechanistic description of the bulk viscous response, with the local structure resetting due to rotational/localized motions on the order of 1-2 ps, approximately three times slower than the relaxations associated with shear viscosity. In this way we show that the shear viscous response is most closely associated with changes in water network connectivity, while the bulk viscous response is associated with local density fluctuations.

Direct observation of o-benzyne formation in photochemical hexadehydro-Diels-Alder (hν-HDDA) reactions.

Reactive ortho-benzyne derivatives are believed to be the initial products of liquid-phase [4 + 2]-cycloadditions between a 1,3-diyne and an alkyne via what is known as a hexadehydro-Diels–Alder (HDDA) reaction. The UV/VIS spectroscopic observation of o-benzyne derivatives and their photochemical dynamics in solution, however, have not been reported previously. Herein, we report direct UV/VIS spectroscopic evidence for the existence of an o-benzyne in solution, and establish the dynamics of its formation in a photoinduced reaction. For this purpose, we investigated a bis-diyne compound using femtosecond transient absorption spectroscopy in the ultraviolet/visible region. In the first step, we observe excited-state isomerization on a sub-10 ps time scale. For identification of the o-benzyne species formed within 50–70 ps, and the corresponding photochemical hexadehydro-Diels–Alder (hν-HDDA) reactions, we employed two intermolecular trapping strategies. In the first case, the o-benzyne was trapped by a second bis-diyne, i.e., self-trapping. The self-trapping products were then identified in the transient absorption experiments by comparing their spectral features to those of the isolated products. In the second case, we used perylene for trapping and reconstructed the spectrum of the trapping product by removing the contribution of irrelevant species from the experimentally observed spectra. Taken together, the UV/VIS spectroscopic data provide a consistent picture for o-benzyne derivatives in solution as the products of photo-initiated HDDA reactions, and we deduce the time scales for their formation.

Coherent charge-phonon correlations and exciton dynamics in orthorhombic CH3NH3PbI3 measured by ultrafast multi-THz spectroscopy.

We use time-resolved multi-terahertz spectroscopy for the range 4-40 meV to probe coherent and incoherent ultrafast charge carrier and exciton dynamics in the low temperature orthorhombic phase of the hybrid metal halide perovskite CH3NH3PbI3. Time- and energy-resolved terahertz reflectivity maps reveal strongly damped but coherent oscillations in the 2-4 THz reststrahlen band, indicating charge coupling to a distribution of low energy phonon modes centered at 0.9 THz (3.7 meV or 30 cm-1). First-principles calculations reveal that these modes are entirely of mixed organic/inorganic sublattice character, with the power spectrum of the coherent oscillations showing a high frequency cutoff just at the onset of organic cation-only vibrations. Two anomalous reflectivity signatures are observed which are not phonon related, which we assign to a free exciton at 12 meV appearing on a 0.5 ps time scale and a defect bound exciton at 29-32 meV appearing on slower 1 ps time scale. Our measurements reveal the coherent coupling of charges to low energy vibrations of mixed sublattice character and the presence of two distinct populations of free and bound excitons at low temperatures.

40 GHz-rate all-optical cross-modulation of core-guided near infrared light in single mode fiber by surface plasmons on gold-coated tilted fiber Bragg gratings

All-optical control of Surface Plasmon Polaritons (SPPs) can switch light with high speed and a large signal to noise ratio. We demonstrate 25 ps-time scale switching of continuous wave light by pump pulses copropagating in the same single mode fiber at different wavelengths near 1550 nm. The switching is due to hot carriers from the SPPs in a 45 nm-thin gold coating on the fiber cladding. The SPPs are generated by pump pulses coupled from the core to cladding modes by a tilted fiber Bragg grating (TFBG). Hot carriers modify the complex permittivity of the metal coating on a time scale of the order of picoseconds and hence the cladding mode resonance wavelengths of the TFBG. A probe light signal copropagating in the same fiber can therefore be modulated by the transmission resonance shifts. With 25 ps pulses at 1540.4 nm and 1 MHz and 50 mW average power, the modulation depth of a CW probe at 1543.4 nm copropagating in the core reached 4.5% ± 1% with a pulse width broadened to 56 ps. Under these conditions, the pump power density was 0.147 GW/cm2 in the metal layer, for a conversion efficiency as high as 30% ± 7% per GW/cm2. Since many other plasmonic and nonlinear active materials can be deposited on fiber claddings, we believe that this very simple all-fiber configuration to perform all-optical switching of core-guided light in single mode fibers by plasmon-modulated resonances has strong potential applications in studies of light-matter interactions over fast and ultrafast time scales.

Thiophenylazobenzene: An Alternative Photoisomerization Controlled by Lone‐Pair⋅⋅⋅π Interaction

AbstractAzoheteroarene photoswitches have attracted attention due to their unique properties. We present the stationary photochromism and ultrafast photoisomerization mechanism of thiophenylazobenzene (TphAB). It demonstrates impressive fatigue resistance and photoisomerization efficiency, and shows favorably separated (E)‐ and (Z)‐isomer absorption bands, allowing for highly selective photoconversion. The (Z)‐isomer of TphAB adopts an unusual orthogonal geometry where the thiophenyl group is perfectly perpendicular to the phenyl group. This geometry is stabilized by a rare lone‐pair⋅⋅⋅π interaction between the S atom and the phenyl group. The photoisomerization of TphAB occurs on the sub‐ps to ps timescale and is governed by this interaction. Therefore, the adoption and disruption of the orthogonal geometry requires significant movement along the inversion reaction coordinates (CNN and NNC angles). Our results establish TphAB as an excellent photoswitch with versatile properties that expand the application possibilities of AB derivatives.

Thiophenylazobenzene: An Alternative Photoisomerization Controlled by Lone-Pair⋅⋅⋅π Interaction.

Azoheteroarene photoswitches have attracted attention due to their unique properties. We present the stationary photochromism and ultrafast photoisomerization mechanism of thiophenylazobenzene (TphAB). It demonstrates impressive fatigue resistance and photoisomerization efficiency, and shows favorably separated (E)‐ and (Z)‐isomer absorption bands, allowing for highly selective photoconversion. The (Z)‐isomer of TphAB adopts an unusual orthogonal geometry where the thiophenyl group is perfectly perpendicular to the phenyl group. This geometry is stabilized by a rare lone‐pair⋅⋅⋅π interaction between the S atom and the phenyl group. The photoisomerization of TphAB occurs on the sub‐ps to ps timescale and is governed by this interaction. Therefore, the adoption and disruption of the orthogonal geometry requires significant movement along the inversion reaction coordinates (CNN and NNC angles). Our results establish TphAB as an excellent photoswitch with versatile properties that expand the application possibilities of AB derivatives.

Ultrafast processes triggered by one- and two-photon excitation of a photochromic and luminescent hydrazone.

In this work we apply a combination of steady state and time resolved luminescence and absorption spectroscopies to investigate the excited-state dynamics of a recently developed molecular photoswitch, belonging to the hydrazone family. The outstanding properties of this molecule, involving fluorescence toggling, bistability, high isomerization quantum yield and non-negligible two-photon absorption cross section, make it very promising for numerous applications. Here we show that the light induced Z/E isomerization occurs on a fast <1 ps timescale in both toluene and acetonitrile, while the excited state lifetime of the Z-form depends on solvent polarity, suggesting a partial charge transfer nature of its low lying excited state. Time-resolved luminescence measurements evidence the presence of a main emission component in the 500–520 nm spectral range, attributed to the Z-isomer, and a very short living blue-shifted emission, attributed to the E-isomer. Finally, transient absorption measurements performed upon far-red excitation are employed as an alternative method to determine the two-photon absorption cross-section of the molecule.

Time-dependent vibrational sum-frequency generation spectroscopy of the air-water interface

Vibrational sum-frequency generation spectroscopy is a powerful method to study the microscopic structure and dynamics of interfacial systems. Here we demonstrate a simple computational approach to calculate the time-dependent, frequency-resolved vibrational sum-frequency generation spectrum (TD-vSFG) of the air-water interface. Using this approach, we show that at the air-water interface, the transition of water molecules with bonded OH modes to free OH modes occurs at a time scale of sim3 ps, whereas water molecules with free OH modes rapidly make a transition to a hydrogen-bonded state within sim2 ps. Furthermore, we also elucidate the origin of the observed differential dynamics based on the time-dependent evolution of water molecules in the different local solvent environments.

Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity.

Ligand substitution reactions are common in solvated transition metal complexes, and harnessing them through initiation with light promises interesting practical applications, driving interest in new means of probing their mechanisms. Using a combination of time-resolved x-ray absorption spectroscopy and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations and x-ray absorption near-edge spectroscopy calculations, we elucidate the mechanism of photoaquation in the model system iron(ii) hexacyanide, where UV excitation results in the exchange of a CN- ligand with a water molecule from the solvent. We take advantage of the high flux and stability of synchrotron x-rays to capture high precision x-ray absorption spectra that allow us to overcome the usual limitation of the relatively long x-ray pulses and extract the spectrum of the short-lived intermediate pentacoordinated species. Additionally, we determine its lifetime to be 19 (±5) ps. The QM/MM simulations support our experimental findings and explain the ∼20 ps time scale for aquation as involving interconversion between the square pyramidal (SP) and trigonal bipyramidal pentacoordinated geometries, with aquation being only active in the SP configuration.

Ultrafast carrier and phonon dynamics in few-layer 2H-MoTe2.

By using femtosecond pump-probe spectroscopy with broadband detection from near-infrared to midinfrared, the carrier and phonon dynamics in few-layer 2H-MoTe2 after ultrafast excitation have been investigated in detail. Immediately following the photoexcitation, an ultrafast relaxation of the generated hot carriers by releasing phonons is observed within hundreds of femtoseconds. The subsequent electron-hole recombination with a time constant of ∼1.5 ps is clearly identified and demonstrated to be mediated through a defect-assisted process. Furthermore, we confirm that the observed redshift of the exciton resonance energy on longer time scales arises from the ultrafast thermalization of the 2H-MoTe2 lattice caused by the transfer of electronic excitation to the phonon system. As a result, the thermalization dynamics of the lattice within 2 ps and the following cooling process of the phonon system on the 100 ps time scale are directly monitored.

Altered Protein Dynamics and Increased Aggregation of Human γS-Crystallin Due to Cataract-Associated Deamidations.

Deamidation is a major age-related modification in the human lens that is highly prevalent in crystallins isolated from the insoluble fraction of cataractous lenses and also causes protein aggregation in vitro. However, the mechanism by which deamidation causes proteins to become insoluble is not known because only subtle structural changes were observed in vitro. We have identified Asn14 and Asn76 of γS-crystallin as highly deamidated in insoluble proteins isolated from aged lenses. These sites are on the surface of the N-terminal domain and were mimicked by replacing the Asn with Asp residues in order to generate recombinant human γS and deamidated mutants. Both N14D and N76D had increased light scattering compared to wild-type γS (WT) and increased aggregation during thermal-induced denaturation. Aggregation was enhanced by oxidized glutathione, suggesting deamidation may increase susceptibility to form disulfide bonds. These changes were correlated to changes in protein dynamics determined by NMR spectroscopy. Heteronuclear NMR spectroscopy was used to measure amide hydrogen exchange and 15N relaxation dynamics to identify regions with increased dynamics compared to γS WT. Residue-specific changes in solvent accessibility and dynamics were both near and distant from the sites of deamidation, suggesting that deamidation had both local and global effects on the protein structure at slow (ms to s) and fast (μs to ps) time scales. Thus, a potential mechanism for γS deamidation-induced insolubilization in cataractous lenses is altered dynamics due to local regions of unfolding and increased flexibility in both the N- and C-terminal domains particularly at surface helices. This conformational flexibility increases the likelihood of aggregation, which would be enhanced in the oxidizing cytoplasm of the aged and cataractous lens. The NMR data combined with the in vivo insolubility and in vitro aggregation findings support a model that deamidation drives changes in protein dynamics that facilitate protein aggregation associated with cataracts.

Ultrafast Charge Separation and Recombination across a Molecule/CsPbBr3 Quantum Dot Interface from First-Principles Nonadiabatic Molecular Dynamics Simulation

All-inorganic perovskite quantum dots (QDs) hold great promise in photovoltaic solar cells. However, the reduced dimensionality of QDs confines the photoexcited electron–hole pairs, suppresses charge separation, and accelerates charge recombination (CR), limiting the photon-to-electron conversion efficiency of a solar cell. Molecule passivation can overcome this shortcoming via efficiently extracting charge carriers from QDs. Using a combination of time-domain density functional theory and nonadiabatic (NA) molecular dynamics, we demonstrate that low-frequency vibrations promoted both charge separation and recombination. The photoexcited excitons on a CsPbBr3 QD can efficiently dissociate into free charge carriers via rapid interfacial electron transfer (ET) and hole transfer (HT) to a binding benzoquinone (BQ) and a phenothiazine (PTZ) molecule on similar sub-100 ps time scales, respectively. This is manifested by the fact that the QD-BQ system holds smaller energy gap and NA coupling between the donor a...

Designing Catalysts for Water Splitting Based on Electronic Structure Considerations

Water splitting involves the synergistic operation of water oxidation and hydrogen evolution half-reactions and remains a considerable challenge since it requires the concerted transfer of four electrons and four protons. Catalysts that can facilitate both of the half-reactions at low overpotentials are imperative to avoid squandering free energy harvested using a semiconductor in a photoelectrochemical cell, or provided directly in the form of current in a water electrolyzer. Photocatalytic water splitting requires the operation of light harvesting, charge separation, charge transport, and redox catalytic steps that must outcompete charge recombination. As such, it requires the precise tunability of energetic offsets to establish optimal thermodynamic driving forces for charge transfer and control of interfaces to mediate kinetics of charge transfer. The talk will focus on the design of compounds with the composition M x V2O5 where M is a post-transition metal cation with lone-pairs characterized by intercalative mid-gap states that can accept holes from photoexcited semiconductor quantum dots. Such compounds, accessible through topochemical intercalation of metastable polymorphs of V2O5, have facilitated the design of heterostructures with energetic offsets primed to facilitate effective hole transfer upon photoexcitation of the heterostructures, thereby mitigating the longstanding challenge of the anodic photocorrosion of quantum dots. Interfacial design further provides a means of modulating the dynamics of hole transfer, which occurs at <1 ps timescales. The second half of the talk will focus on discussing the specific electronic structure characteristics of edge sites of MoS2 that enable them to function as catalysts for the hydrogen evolution reaction. Interfacial hybridization of MoS2 with nC60 provides a means to modulate the electronic structure and enhance catalytic activity. Interfacing MoS­2 with semiconductor quantum dots further yields effective photocatalysts for hydrogen evolution that have been examined using operando X-ray absorption spectroscopy. The two examples illustrate the potential of computationally driven materials design to unravel new physical insights and provide practical solutions to challenges in hydrogen generation. The authors acknowledge support from the NSF under DMREF-1627197, DMREF-1626967, and DMREF-1627583 as well as from the NSF DMREF/ DOE EERE EMN project.