Femtosecond Pump-probe Spectroscopy Research Articles

Fluorescence and excited state dynamics of the deprotonated Schiff base retinal in proteorhodopsin.

The UV light absorbing species of proteorhodopsin with deprotonated Schiff base retinal was investigated using steady-state fluorescence and femtosecond pump-probe spectroscopy. Compared to the all-trans retinal with protonated Schiff base, the deprotonated chromophore absorbs at 365 nm and exhibits a blue-shifted fluorescence spectrum. The unusually long-lived excited state decays bi-exponentially with time constants of 8 ps and 130 ps to form a deprotonated 13-cis retinal as the primary photo-product.

Nonequilibrium carrier dynamics in ultrathin Si-on-glass films

We present a femtosecond pump-probe spectroscopy approach for characterization of amorphous and microcrystalline silicon films grown on glass substrates. Such films are presently being considered as absorbers in tandem-type, Si-based photovoltaic cells. Our experiments consisted of time-resolved, two-colour femtosecond optical measurements, performed in the transmission mode in a wide range of delay times. Depending on the sample growth process, collected normalized transmissivity change (ΔT/T) waveforms exhibited a bi-exponential relaxation dynamics with the characteristic times varying from picoseconds to nanoseconds. Experimental data were interpreted using a three-rate-equation models, and the relaxation was identified as, depending on the Si film type, being dominated by either carrier trapping or electron-phonon cooling and followed by electron-hole recombination. An excellent fit between the model and the ΔT/T transients was obtained and a correlation between the Si film growth process, its hydrogen content, and the associated trap concentration was demonstrated.

Time-resolved and XUV spectroscopy of helium nanodroplets

SynopsisThe ultrafast dynamics of pure and doped helium nanodroplets is studied using VIS and XUV femto-second pump-probe spectroscopy in combination with ion and electron imaging detection.

Low frequency dynamics of the nitrogenase MoFe protein via femtosecond pump probe spectroscopy — Observation of a candidate promoting vibration

We have used femtosecond pump-probe spectroscopy (FPPS) to study the FeMo-cofactor within the nitrogenase (N2ase) MoFe protein from Azotobacter vinelandii. A sub-20-fs visible laser pulse was used to pump the sample to an excited electronic state, and a second sub-10-fs pulse was used to probe changes in transmission as a function of probe wavelength and delay time. The excited protein relaxes to the ground state with a ~1.2ps time constant. With the short laser pulse we coherently excited the vibrational modes associated with the FeMo-cofactor active site, which are then observed in the time domain. Superimposed on the relaxation dynamics, we distinguished a variety of oscillation frequencies with the strongest band peaks at ~84, 116, 189, and 226cm−1. Comparison with data from nuclear resonance vibrational spectroscopy (NRVS) shows that the latter pair of signals comes predominantly from the FeMo-cofactor. The frequencies obtained from the FPPS experiment were interpreted with normal mode calculations using both an empirical force field (EFF) and density functional theory (DFT). The FPPS data were also compared with the first reported resonance Raman (RR) spectrum of the N2ase MoFe protein. This approach allows us to outline and assign vibrational modes having relevance to the catalytic activity of N2ase. In particular, the 226cm−1 band is assigned as a potential ‘promoting vibration’ in the H-atom transfer (or proton-coupled electron transfer) processes that are an essential feature of N2ase catalysis. The results demonstrate that high-quality room-temperature solution data can be obtained on the MoFe protein by the FPPS technique and that these data provide added insight to the motions and possible operation of this protein and its catalytic prosthetic group.

Near infrared ultrafast pump-probe spectroscopy with ZrF4-BaF2-LaF3-AlF3-NaF fiber supercontinuum

We report on the performance of a setup designed for femtosecond pump-probe spectroscopy in the near infrared (NIR) spectral region. We generate a supercontinuum (SC) probe by coupling 140 fs light pulses at 1550 nm into a ZrF4-BaF2-LaF3-AlF3-NaF (ZBLAN) fiber. The combined high nonlinearity and transparency of the ZBLAN fluoride glass allows us to obtain a SC probe from 1 to 2.6 μm. The NIR pulses are used to demonstrate a proof of principle experiment probing the relaxation of photo induced excitations in a conjugated polymer:fullerene blend film. The results show the possibility to perform fibre based NIR SC femtosecond spectroscopy at >100 KHz repetition rate and using lasers with pulse energy just above 300 nJ.

Photoinduced switching to metallic states in the two-dimensional organic Mott insulator dimethylphenazine-tetrafluorotetracyanoquinodimethane with anisotropic molecular stacks

A photoinduced phase transition was investigated in an organic charge-transfer (CT) complex ${\mathrm{M}}_{2}\mathrm{P}\ensuremath{-}\mathrm{TCNQ}{\mathrm{F}}_{4}, [{\mathrm{M}}_{2}\mathrm{P}$: 5,10-dihydro-5,10-dimethylphenazine, donor (D) molecule; $\mathrm{TCNQ}{\mathrm{F}}_{4}$: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, acceptor (A) molecule] by means of femtosecond pump-probe reflection spectroscopy. This is an ionic compound and has a peculiar two-dimensional (2D) molecular arrangement; the same A (or D) molecules arrange along the [100] direction, and A and D molecules alternately arrange along the [111] direction. It results in a strongly anisotropic two-dimensional electronic structure. This compound shows a structural and magnetic phase transition at 122 K below which the two neighboring molecules are dimerized along both the [100] and [111] directions. We demonstrate that two kinds of photoinduced phase transitions occur by irradiation of a femtosecond laser pulse; in the high-temperature lattice-uniform phase, a quasi-one-dimensional (1D) metallic state along the AA(DD) stack is generated, and in the low-temperature lattice-dimerized phase, a quasi-2D metallic state is initially produced and molecular dimerizations are subsequently released. Mixed-stack CT compounds consisting of DA stacks are generally insulators or semiconductors in the ground state. Here, such a dynamical metallization in the DA stack is demonstrated. The release of the dimerizations drives several kinds of coherent oscillations which play an important role in the stabilization of the lattice-dimerized phase. The mechanisms of those photoinduced phase transitions are discussed in terms of the magnitudes of the anisotropic bandwidths and molecular dimerizations along two different directions of the molecular stacks.

Polarization dependence of coherent phonon generation and detection in the three-dimensional topological insulatorBi2Te3

We have studied the polarization dependence of coherent phonons in the topological insulator Bi2Te3. Using polarization-dependent femtosecond pump-probe spectroscopy, we measured coherent phonons as a function of angle when the pump and probe polarizations were fixed, and the crystal orientation was rotated. For isotropic detection, depending on the spot position, oscillations either from only low- and high-frequency phonons of A1g symmetry, or in addition from the mode at 3.6 THz were observed. All the modes were found to be independent of the orientation of electric field vector with respect to the crystal axes testifying to their full symmetry while no modes of lower symmetry appeared in any polarization geometry. For anisotropic detection both modes of Eg symmetry could be detected, but their amplitudes were considerably smaller than those of A1g symmetry. To clarify the coherent phonon assignment and the process of coherent phonon generation in Bi2Te3, the time-domain measurements were complemented by spontaneous Raman scattering. The comparison of frequency- and time-domain results and the polarization dependence suggest that the 3.6 THz mode belongs to crystalline Te arising due to tellurium segregation. A discrepancy between the time- and frequency domain data is discussed.

Correlating photoacidity to hydrogen-bond structure by using the local O-H stretching probe in hydrogen-bonded complexes of aromatic alcohols.

To assess the potential use of O-H stretching modes of aromatic alcohols as ultrafast local probes of transient structures and photoacidity, we analyze the response of the O-H stretching mode in the 2-naphthol-acetonitrile (2N-CH3CN) 1:1 complex after UV photoexcitation. We combine femtosecond UV-infrared pump-probe spectroscopy and a theoretical treatment of vibrational solvatochromic effects based on the Pullin perturbative approach, parametrized at the density functional theory (DFT) level. We analyze the effect of hydrogen bonding on the vibrational properties of the photoacid-base complex in the S0 state, as compared to O-H stretching vibrations in a wide range of substituted phenols and naphthols covering the 3000-3650 cm(-1) frequency range. Ground state vibrational properties of these phenols and naphthols with various substituent functional groups are analyzed in solvents of different polarity and compared to the vibrational frequency shift of 2N induced by UV photoexcitation to the (1)Lb electronic excited state. We find that the O-H stretching frequency shifts follow a linear relationship with the solvent polarity function F0 = (2ε0 - 2)/(2ε0 + 1), where ε0 is the static dielectric constant of the solvent. These changes are directly correlated with photoacidity trends determined by reported pKa values and with structural changes in the O···N and O-H hydrogen-bond distances induced by solvation or photoexcitation of the hydrogen-bonded complexes.

Discontinuous variation of the surface plasmon linewidth of small sodium nanoparticles with electron temperatures

We found a novel behavior of the surface plasmon linewidth of small sodium nanoparticles, which monotonically decreases with the electron temperature and bears a sudden drop or rise at high electron temperatures. Our calculation is based on the model constructed by splitting the total Hamiltonian of all valence electrons of a metallic nanoparticle into two sub-Hamiltonians and the coupling between them. This novel behavior of the surface plasma resonance linewidth can be verified by pump-probe femtosecond spectroscopy experiments and is able to take place for metallic particles with sizes less than few nanometers. In addition, we propose that it is the size uncertainty of small nanoparticles that yields the intrinsic linewidth of the surface plasmon resonance, which is supported by experimental and theoretical results of nanoparticles Na8 and Na20.

Photocarrier dynamics in CIGS, CZTS, and related materials revealed by ultrafast optical spectroscopy

We discuss the photocarrier dynamics in emerging thin‐film solar‐cell materials, Cu(In,Ga)Se2 (CIGS), Cu2ZnSnS4 (CZTS), and CdTe‐based nanocrystals (NCs), using time‐resolved photoluminescence and femtosecond pump–probe spectroscopy. In CIGS and CZTS samples, we found long‐lived free photocarriers and slow intraband relaxation at room temperature. These distinctive behaviors of the free carriers are considered common features in multinary semiconductors and are related to the complicated near‐band edge structure due to potential fluctuations, which might affect solar‐cell efficiencies. We revealed the relationship in CdTe‐based type‐II NCs between hot carrier transfer and intraband relaxation, providing a better understanding of the charge separation mechanism in multinary semiconductors. We also demonstrated the usefulness of ultra‐fast optical spectroscopy techniques for clarifying the photocarrier dynamics in various semiconducting bulk and nano‐structure materials for solar cells.

Ultrafast excited-state charge-transfer dynamics in laccase type I copper site

Femtosecond pump–probe spectroscopy was used to investigate the excited state dynamics of the T1 copper site of laccase from Pleurotus ostreatus, by exciting its 600nm charge transfer band with a 15-fs pulse and probing over a broad range in the visible region. The decay of the pump-induced ground-state bleaching occurs in a single step and is modulated by clearly visible oscillations. Global analysis of the two-dimensional differential transmission map shows that the excited state exponentially decays with a time constant of 375fs, thus featuring a decay rate slower than those occurring in quite all the investigated T1 copper site proteins. The ultrashort pump pulse induces a vibrational coherence in the protein, which is mainly assigned to ground state activity, as expected in a system with fast excited state decay. Vibrational features are discussed also in comparison with the traditional resonance Raman spectrum of the enzyme. The results indicate that both excited state dynamics and vibrational modes associated with the T1 Cu laccase charge transfer have main characteristics similar to those of all the T1 copper site-containing proteins. On the other hand, the differences observed for laccase from P. ostreatus further confirm the peculiar hypothesized trigonal T1 Cu site geometry.

Excited state dynamics and isomerization in ruthenium sulfoxide complexes.

Molecular photochromic compounds are those that interconvert between two isomeric forms with light. The two isomeric forms display distinct electronic and molecular structures and must not be in equilibrium with one another. These light-activated molecular switch compounds have found wide application in areas of study ranging from chemical biology to materials science, where conversion from one isomeric form to another by light prompts a response in the environment (e.g., protein or polymeric material). Certain ruthenium and osmium polypyridine sulfoxide complexes are photochromic. The mode of action is a phototriggered isomerization of the sulfoxide from S- to O-bonded. The change in ligation drastically alters both the spectroscopic and electrochemical properties of the metal complex. Our laboratory has pioneered the preparation and study of these complexes. In particular, we have applied femtosecond pump-probe spectroscopy to reveal excited state details of the isomerization mechanism. The data from numerous complexes allowed us to predict that the isomerization was nonadiabatic in nature, defined as occurring from a S-bonded triplet excited state (primarily metal-to-ligand charge transfer in character) to an O-bonded singlet ground state potential energy surface. This prediction was corroborated by high-level density functional theory calculations. An intriguing aspect of this reactivity is the coupling of nuclear motion to the electronic wave function and how this coupling affects motions productive for isomerization. In an effort to learn more about this coupling, we designed a project to examine phototriggered isomerization in bis-sulfoxide complexes. The goal of these studies was to determine whether certain complexes could be designed in which a single photon excitation event would prompt two sulfoxide isomerizations. We employed chelating sulfoxides in this study and found that both the nature of the chelate ring and the R group on the sulfoxide affect the photochemical reactivity. For example, this reactivity may be tuned such that two sulfoxide ligands isomerize sequentially following two successive excitations or that two sulfoxide ligands isomerize following a single excitation. This Account explains our understanding to date of this photochemistry.

Ultrafast charge and lattice dynamics in one-dimensional Mott insulator of CuO-chain compoundCa2CuO3investigated by femtosecond absorption spectroscopy

Charge dynamics in one-dimensional (1D) Mott insulators was investigated by femtosecond pump-probe absorption spectroscopy on ${\mathrm{Ca}}_{2}{\mathrm{CuO}}_{3}$. An irradiation of a femtosecond laser pulse gives rise to a Drude-like response due to the nature of spin-charge separation characteristic of 1D Mott insulators. The photoinduced metallic state decays with \ensuremath{\sim}30 fs, and photocarriers are localized as polarons via charge-phonon coupling which produce a broad midgap absorption. Calculations with the extended Hubbard-Holstein model suggest that the peak structure of the midgap absorption is a magnon sideband of the polaron absorption. This demonstrates that charge-spin coupling becomes effective via charge-phonon coupling in polarons.

Predissociation dynamics of lithium iodide.

The predissociation dynamics of lithium iodide (LiI) in the first excited A-state is investigated for molecules in the gas phase and embedded in helium nanodroplets, using femtosecond pump-probe photoionization spectroscopy. In the gas phase, the transient Li(+) and LiI(+) ion signals feature damped oscillations due to the excitation and decay of a vibrational wave packet. Based on high-level ab initio calculations of the electronic structure of LiI and simulations of the wave packet dynamics, the exponential signal decay is found to result from predissociation predominantly at the lowest avoided X-A potential curve crossing, for which we infer a coupling constant VXA = 650(20) cm(-1). The lack of a pump-probe delay dependence for the case of LiI embedded in helium nanodroplets indicates fast droplet-induced relaxation of the vibrational excitation.

Ultrafast excitation energy transfer from encapsulated quaterrylene to single-walled carbon nanotube

We investigate excitation energy transfer from an encapsulated quaterrylene molecule to a single-walled carbon nanotube by means of femtosecond pump-probe spectroscopy. The time constant of energy transfer becomes shorter with increasing average diameter of nanotube: 1.4±0.2ps for 1.0nm, 1.1±0.2ps for 1.4nm, and 0.4±0.1ps for 1.8nm. The observed behavior is discussed considering the distance of less than 1nm between the molecule and the nanotube wall.

Charge separation in supramolecular ferrocene(s)-zinc porphyrin-fullerene triads: A femtosecond transient absorption study

Mechanistic aspects of photoinduced charge separation in supramolecular triads, constructed using covalently linked zinc porphyrin-ferrocene(s) dyads — self-assembled via axial coordination to either pyridine or phenylimidazole appended fulleropyrrolidine ( Fc x- ZnP : PyC 60 or Fc x- ZnP : ImC 60; x = 1 or 2), has been investigated using femtosecond pump-probe transient spectroscopy. Upon photoexcitation of ZnP , charge separation from ferrocene to 1 ZnP * to yield the initial Fc +- ZnP •-: C 60 radical ion-pair or charge separation from 1 ZnP * to C 60 to yield the initial Fc - ZnP •+: C 60•- radical ion-pair, depending upon the ferrocene-zinc porphyrin intermolecular distance, was observed. These radical ion-pairs resulted in the formation of ultimate distantly separated Fc +- ZnP : C 60•- radical ion-pairs either via an electron migration (former case) or hole shift (latter case) process. Kinetics of charge separation as a function of spacer connecting the ferrocene and porphyrin, and spacer between the porphyrin and fullerene is reported. In agreement with our earlier study (J. Phys. Chem. B 2004; 108: 11333–11343), the Fc +- ZnP : C 60•- radical ion-pair persisted beyond the monitoring time window of our instrument, suggesting charge stabilization in these supramolecular triads.

Bringing light into the dark triplet space of molecular systems.

A molecule or a molecular system always consists of excited states of different spin multiplicities. With conventional optical excitations, only the (bright) states with the same spin multiplicity of the ground state could be directly reached. How to reveal the dynamics of excited (dark) states remains the grand challenge in the topical fields of photochemistry, photophysics, and photobiology. For a singlet-triplet coupled molecular system, the (bright) singlet dynamics can be routinely examined by conventional femtosecond pump-probe spectroscopy. However, owing to the involvement of intrinsically fast decay channels such as intramolecular vibrational redistribution and internal conversion, it is very difficult, if not impossible, to single out the (dark) triplet dynamics. Herein, we develop a novel strategy that uses an ultrafast broadband white-light continuum as a excitation light source to enhance the probability of intersystem crossing, thus facilitating the population flow from the singlet space to the triplet space. With a set of femtosecond time-reversed pump-probe experiments, we report on a proof-of-concept molecular system (i.e., the malachite green molecule) that the pure triplet dynamics can be mapped out in real time through monitoring the modulated emission that occurs solely in the triplet space. Significant differences in excited-state dynamics between the singlet and triplet spaces have been observed. This newly developed approach may provide a useful tool for examining the elusive dark-state dynamics of molecular systems and also for exploring the mechanisms underlying molecular luminescence/photonics and solar light harvesting.

Self-trapped excitons on the surface of Si nanocrystals in SiO2

The experimental data recently obtained by the femtosecond pump-probe spectroscopy technique have shown that the self-trapped exciton (STE) state plays a key role in the dynamics of hot excitons in photoexcited silicon nanocrystals embedded in a SiO matrix. We present a theoretical model of excitons self-trapped on Si–O bounds at the silicon nanocrystal surface. The thermally activated transition from the STE state to the nanocrystal has been studied. The nonradiative multiphonon recombination of the STE initiated by the interaction with vibrations of local dipoles in a amorphous SiO matrix has been considered, too. The relaxation process of “hot” carriers localized in Si nanocrystals has been modulated using Monte Carlo simulation. We have demonstrated that effective exchange between the STE states and “hot” free exciton states opens the new way of the energy relaxation and leads to the wide energy distribution of the hot carriers during 10–100 ps after excitation.

Ultrafast Dynamics of Electrons in Ammonia

Solvated electrons were first discovered in solutions of metals in liquid ammonia. The physical and chemical properties of these species have been studied extensively for many decades using an arsenal of electrochemical, spectroscopic, and theoretical techniques. Yet, in contrast to their hydrated counterpart, the ultrafast dynamics of ammoniated electrons remained completely unexplored until quite recently. Femtosecond pump-probe spectroscopy on metal-ammonia solutions and femtosecond multiphoton ionization spectroscopy on the neat ammonia solvent have provided new insights into the optical properties and the reactivities of this fascinating species. This article reviews the nature of the optical transition, which gives the metal-ammonia solutions their characteristic blue appearance, in terms of ultrafast relaxation processes involving bound and continuum excited states. The recombination processes following the injection of an electron via photoionization of the solvent are discussed in the context of the electronic structure of the liquid and the anionic defect associated with the solvated electron.

Synthesis and Photophysics of Quaterrylene Molecules in Single-Walled Carbon Nanotubes: Excitation Energy Transfer between a Nanoscale Cylinder and Encapsulated Molecules

We report the synthesis of quaterrylene monomers and dimers from perylene inside single-walled carbon nanotubes (SWNTs). Excitation energy transfer (EET) from the encapsulated molecule to the SWNT is investigated by using femtosecond pump–probe spectroscopy and time-resolved luminescence spectroscopy. Optical spectroscopy and transmission electron microscopy reveal the molecular arrangement of quaterrylene monomers and dimers within the SWNTs. The observed EET time from the dipole-allowed excited state of the quaterrylene monomer to the SWNT depends on the tube diameter and is found to be 1.1 ± 0.2 ps and 0.4 ± 0.1 ps for average diameters of 1.4 and 1.8 nm, respectively. These transfer times are ascribed to EET via a Coulomb interaction between transition dipoles. The transfer time from the dipole-forbidden state of the dimer to the SWNT with an average diameter of 1.8 nm is 3.8 ± 0.2 ps. The EET mechanism presumably corresponds to electron exchange or Coulomb interactions involving higher multipoles.