Ultrafast Infrared Transient Absorption Spectroscopy of Ni(CO)4 Photodissociation.
Abstract not provided.
Cole-Filipiak, Neil↗
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Coherent electronic-vibrational dynamics in deuterium bromide probed via attosecond transient-absorption spectroscopy
Ultrafast laser excitation can trigger multiplex coherent dynamics in molecules. Here, we report attosecond transient-absorption experiments addressing simultaneous probing of electronic and vibrational dynamics in a prototype molecule, deuterium bromide (DBr), following its strong-field ionization. Electronic and vibrational coherences in the ionic X$^2\Pi_{3/2}$ and X$^2\Pi_{1/2}$ states are characterized in the Br-$3d$ core-level absorption spectra via quantum beats with 12.6-fs and 19.9-fs periodicities, respectively. Polarization scans reveal that the phase of the electronic quantum beats depends on the probe direction, experimentally showing that the coherent electronic motion corresponds to the oscillation of the hole density along the ionization-field direction. The vibrational quantum beats are found to maintain a relatively constant amplitude, whereas the electronic quantum beats exhibit a partial decrease in time. Quantum wave-packet simulations show that the decoherence effect from the vibrational motion is insignificant because of the parallel relation between the X$^2\Pi_{3/2}$ and X$^2\Pi_{1/2}$ potentials. Finally, a comparison between the DBr and HBr results suggests that rotation motion is responsible for the decoherence since it leads to initial alignment prepared by the strong-field ionization.
74 ATOMIC AND MOLECULAR PHYSICS↗
Time-resolved absorption spectroscopic characterization of ultrafast laser-produced plasmas under varying background pressures
Time-resolved tunable laser absorption spectroscopy is used to characterize the physical properties of ultrafast laser-produced plasmas. The plasmas were produced from an Inconel target, with = 0.4 wt. % Al, using ~ 35 fs, ~800 nm laser pulses at varying Ar background pressures from 1-100 Torr. The absorption spectrum of atomic Al is measured with high spectral and temporal resolution when the probe laser is stepped across the selected Al transition at 394.4 nm. Spectral fitting is used to infer linewidths, kinetic temperature, Al column density, and pressure broadening coefficient. The late time physical properties of plasmas are compared for various pressure levels. Our studies highlight that a significant lower state population exists even at early times of ultrafast laser-produced plasma evolution and lower state population persistence decreases with increasing ambient pressure. We also show that the fundamental optical properties, such as pressure-broadening, can be measured using ultrafast laser-produced plasmas combined with laser absorption spectroscopy.
laser absorption spectroscopy, laser produced plas↗
Excited State Covalency, Dynamics, and Photochemistry of Square Planar Ni-Thiolate Complexes Revealed by Ultrafast X-ray Absorption
Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal–ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. Here, we investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here [Ni(mpo) 2 ] (mpo = 2-mercaptopyridine- N-oxide) provides a representative example for the larger chemical class and is an active electro- and photo-catalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo) 2 ] is presented based on ultrafast transient X- ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo) 2 ] − ) and relaxation to a pseudo-tetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.
Lim, Hyeongtaek [SLAC National Accelerator Laborat↗
Time-resolved x-ray absorption spectroscopy probe in ultrafast surface chemistry
To celebrate the scientific achievement of Jo Stöhr, I present here a personal account of the use of x-ray absorption spectroscopy to probe dynamics on surfaces using x-ray lasers. In particular, I will review the investigation of ultrafast processes in adsorbates on surfaces using an optical pump and an x-ray absorption spectroscopy probe. Here, it is shown that it is possible to gain insight into the effects of electronic excitations in metals on adsorbates as well as laser-induced vibrational motions. Furthermore, the ultrafast optical pump allows the detection of the CO precursor state in the desorption channel, species close to the transition state in CO oxidation, and the transient HCO intermediate during CO hydrogenation on Ru(0001).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Excited-state structural conformations of Fe-amido photosensitizers revealed by picosecond X-ray absorption spectroscopy
Ultrafast X-ray spectroscopy and modelling were used to characterize distortions in the photo-generated quintet state of Fe sensitizers bearing hybrid N-heterocycle/amido ligands. Photoexcitation induces a 0.10–0.35 Å Fe–N elongation that is smaller for d(Fe–N amido ) compared to d(Fe-N heterocycle ), suggesting that the partial expansion of the Fe–N bonds involving the N-heterocyclic ligands is critical to the rapid population of ligand-field states.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B 12 Coenzymes Controlled by the Axial Base
Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.04 to 0.05 Å. The 5-coordinate base-off cob(II)alamin that is formed following photodissociation has a structure similar to that of the 5-coordinate base-on cob(II)alamin, with a ring expansion of 0.03 to 0.04 Å and a contraction of the lower axial bond length relative to that in the 6-coordinate ground state. Here these data provide insights into the role of the lower axial ligand in modulating the reactivity of B 12 coenzymes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Elucidating Norrish type I reactive pathways by ultrafast X-ray absorption spectroscopy
Norrish type I reactions selectively cleave carbon–carbon bonds directly adjacent to carbonyl groups. Despite their broad use in combination with aromatic carbonyls for additive manufacturing and dental UV curing applications, the nature of the photochemically active state and its population mechanism remain insufficiently understood. Detailed mechanistic insight requires mapping of the photoexcited population flow involving internal conversion and intersystem crossing. We present a time-domain study of gas phase acetophenone as a prototypical aromatic carbonyl combining soft X-ray time-resolved near-edge X-ray absorption fine structure (TR-NEXAFS) spectroscopy at the oxygen K-edge with ab initio multiple spawning (AIMS) simulations. Exploiting the specific sensitivity of TR-NEXAFS spectroscopy to states with nπ* character, we observe population transfer from the initially excited 1 ππ* state to the 1 nπ* state with a time constant of (0.13 ± 0.02) ps after an initial induction period of (0.12 ± 0.02) ps without population transfer, in quantitative agreement with the AIMS simulations. The population in the 1 nπ* state subsequently decays via intersystem crossing, likely mediated by a 3 ππ* state, within (3.17 ± 0.66) ps to a long-lived 3 nπ* state, which is presumed to be active towards Norrish type I chemistry.
Graßl, Martin [SLAC National Accelerator Laborator↗
New Constraints on the Melting Temperature and Phase Stability of Shocked Iron up to 270 GPa Probed by Ultrafast X-Ray Absorption Spectroscopy
Studying the properties and phase diagram of iron at high-pressure and high-temperature conditions has relevant implications for Earth’s inner structure and dynamics and the temperature of the inner core boundary (ICB) at 330 GPa. Also, a hexagonal-closed packed to body-centered cubic (bcc) phase transition has been predicted by many theoretical works but observed only in a few experiments. The recent coupling of high-power laser with advanced x-ray sources from synchrotrons allows for novel approaches to address these issues. Here, we present a study on shock compressed iron up to 270 GPa and 5800 K probed by single-pulse (100 ps FWHM) x-ray absorption spectroscopy (XAS). Based on the analysis of the XAS spectra, we provide structural identification and bulk temperature measurements along the Hugoniot up to the melting. These results rule out the predicted transition to a high-temperature bcc phase and allow one to discriminate among existing equations of state models and melting curves. In particular, we report the first bulk temperature measurement in shock compressed iron on the melting plateau at 240(20) GPa and 5345(600) K. The melting curve resulting from our work extrapolates to a temperature of 6202(514) K at 330 GPa and represents a refined upper bound for the ICB temperature. Published by the American Physical Society 2024
Balugani, S.↗
Ultrashort XUV pulse absorption spectroscopy of partially oxidized cobalt nanoparticles
High-order harmonic generation (HHG) based transient extreme ultraviolet (XUV) absorption spectroscopy is an emerging technique to trace photoinduced charge carrier dynamics in condensed phase materials with femtosecond and even attosecond temporal resolution and elemental specificity. However, its application to nanoparticulate samples that are relevant, for example, for novel photocatalytic light harvesting concepts, has been limited. This is in part due to the challenge to produce residual-free samples on ultrathin, XUV-transparent substrates as well as a widespread understanding that sparsely distributed nanoparticles do not provide sufficient contrast for XUV absorption measurements. Here, we present static XUV absorption spectra of partially oxidized Co nanowire-structures with diameters of approximately 4.5 nm and lengths between 10 and 40 nm, recorded with an ultrashort pulse HHG light source. Nanoparticles are synthesized by the agglomeration of Co atoms inside superfluid helium droplets, followed by surface deposition and oxidation in ambient air. The method is uniquely suited for residual-free synthesis of transition metal nanowires and their deposition on ultrathin substrates. Analysis by high-resolution transmission electron microscopy reveals the formation of CoO nanowires with regions of unoxidized Co in their interior. The nanoparticle samples are investigated in an HHG-driven ultrafast XUV absorption setup. Despite the low surface coverage of only 23%, the recorded spectrum exhibits a distinct absorption feature at the Co M 2,3 (2p) edge near 60 eV with a peak height of about 40 mOD. Finally, the results support the feasibility of table-top ultrafast transient XUV absorption studies of photoinduced dynamics in transition metal oxide nanoparticles with sub-monolayer surface coverage.
74 ATOMIC AND MOLECULAR PHYSICS↗
Adaptive noise canceling for transient absorption microscopy
Significance: Ultrafast fiber lasers are an attractive alternative to bulk lasers for nonlinear optical microscopy for their compactness and low cost. The high relative intensity noise (RIN) of these lasers poses a challenge for pump-probe measurements such as transient absorption and stimulated Raman scattering, along with modalities that provide label-free contrast from the vibrational and electronic structure of molecules. Aim: Digital adaptive filtering was applied to determine the applicability for canceling laser RIN in a transient absorption microscope with an ultrafast fiber laser source. Approach: Digitized signals from the transmitted probe and reference photodetectors were fed to an adaptive filter in MATLAB, running in a noise canceling configuration. This result was then fed to a software lock-in algorithm to demodulate the pump-probe signal. Images were built up one line scan at a time with a 3.5-kHz resonant scanner, with 100× averaging. The imaging target was Bi4Ge3O12, which exhibits nondegenerate two-photon absorption at the pump/probe wavelengths used (530-nm pump and 490-nm probe). Results: Without adaptive noise cancellation, the lock-in output primarily passes the laser RIN within its detection bandwidth, resulting in images that closely follow the linear transmissivity and lack sensitivity to pump-probe time delay. With adaptive noise cancellation in front of the lock-in, the RIN rejection is enough to restore the z-sectioning and sensitivity to pump-probe delay, as expected for transient absorption. Results were limited primarily by noise from the photodetector and analog-to-digital converter. Conclusions: Digital adaptive noise cancellation, even when limited by electronics noise, can recover pump-probe signals by removal of laser RIN, under conditions where averaging alone fails.
42 ENGINEERING↗
Functional Connectivity of Red Chlorophylls in Cyanobacterial Photosystem I Revealed by Fluence-Dependent Transient Absorption
External stressors modulate the oligomerization state of photosystem I (PSI) in cyanobacteria. The number of red chlorophylls (Chls), pigments lower in energy than the P700 reaction center, depends on the oligomerization state of PSI. Here, we use ultrafast transient absorption spectroscopy to interrogate the effective connectivity of the red Chls in excitonic energy pathways in trimeric PSI in native thylakoid membranes of the model cyanobacterium Synechocystis sp. PCC 6803, including emergent dynamics, as red Chls increase in number and proximity. Fluence-dependent dynamics indicate singlet–singlet annihilation within energetically connected red Chl sites in the PSI antenna but not within bulk Chl sites on the picosecond time scale. These data support picosecond energy transfer between energetically connected red Chl sites as the physical basis of singlet–singlet annihilation. The time scale of this energy transfer is faster than predicted by Förster resonance energy transfer calculations, raising questions about the physical mechanism of the process. Our results indicate distinct strategies to steer excitations through the PSI antenna; the red Chls present a shallow reservoir that direct excitations away from P 700 , extending the time to trapping by the reaction center.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sterically Encumbered Heteroleptic Copper(I) β-Diketiminate Complexes with Extended Excited-State Lifetimes
One of the main challenges in developing effective copper(I) photosensitizers is their short excited-state lifetimes, usually attributed to structural distortion upon light excitation. We have previously introduced copper(I) charge-transfer chromophores of the general formula Cu(N^N)(ArNacNac), where N^N is a conjugated diimine ligand and ArNacNac is a substituted β-diketiminate ligand. These chromophores were promising regarding their tunable redox potentials and intense visible absorption but were ineffective as photosensitizers, presumably due to short excited-state lifetimes. Here, we introduce sterically crowded analogues of these heteroleptic chromophores with bulky alkyl substituents on the N^N and/or ArNacNac ligand. Structural analysis was combined with electrochemical and photophysical characterization, including ultrafast transient absorption (UFTA) spectroscopy to investigate the effects of the alkyl groups on the excited-state lifetimes of the complexes. The molecular structures determined by single-crystal X-ray diffraction display more distortion in the ground state as alkyl substituents are introduced into the phenanthroline or the NacNac ligand, showing smaller τ 4 values due to the steric hindrance. UFTA measurements were carried out to determine the excited-state dynamics. Sterically encumbered Cu5 and Cu6 display excited-state lifetimes 15–20 times longer than unsubstituted complex Cu1, likely indicating that the incorporation of bulky alkyl substituents inhibits the pseudo-Jahn–Teller (PJT) flattening distortion in the excited state. Furthermore, this work suggests that the steric properties of these heteroleptic copper(I) charge-transfer chromophores can be readily modified and that the excited-state dynamics are strongly responsive to these modifications.
14 SOLAR ENERGY↗
The Impact of Carotenoid Energy Levels on the Exciton Dynamics and Singlet–Triplet Annihilation in Isolated Bacterial Light-Harvesting 2 Complexes
The light-harvesting 2 (LH2) complex of purple phototrophic bacteria plays a critical role in absorbing solar energy and distributing the excitation energy. Exciton dynamics within LH2 complexes are controlled by the structural arrangement and energy levels of the bacteriochlorophyll (BChl) and carotenoid (Car) pigments. However, there is still debate over the competing light-harvesting versus energy-dissipation pathways. In this work, we compared five variants of the LH2 complex from genetically modified strains of Rhodobacter sphaeroides, all containing the same BChls but different Cars with increasing conjugation: zeta-carotene (N = 7; LH2 Zeta ), neurosporene (N = 9; LH2 Neu ), spheroidene (N = 10; LH2 Spher ), lycopene (N = 11; LH2 Lyco ), and spirilloxanthin (N = 13; LH2 Spir ). Absorption measurements confirmed that the Car excited-state energy decreased with increasing conjugation. Similarly, fluorescence spectra showed that the B850 BChl emission peak had an increasing red shift from LH2 Zeta →(LH2 Neu /LH2 Spher )→LH2 Lyco →LH2 Spir . In contrast, time-resolved fluorescence and ultrafast transient absorption (fs-TA) revealed similar excited-state lifetimes (∼1 ns) for all complexes except LH2 Spir (∼0.7 ns). From fs-TA analysis, an additional ∼7 ps nonradiative dissipation step from B850 BChl was observed for LH2 Zeta . Further, singlet− singlet and singlet−triplet annihilation studies showed a ∼50% average fluorescence lifetime reduction in LH2Zeta at high laser power and high repetition rate, compared to ∼10−15% reductions in LH2 Neu /LH2 Spher /LH2 Lyco and minimal lifetime change in LH2 Spir . In LH2 Zeta , the fastest decay component (<50 ps) became prominent at high repetition rates, consistent with strong singlet−triplet annihilation. Nanosecond TA measurements revealed long-lived (>40 μs) BChl triplet states in LH2 Zeta and signs of damage caused by singlet oxygen, whereas other LH2s showed faster triplet quenching (∼18 ns) by Cars. These findings highlight a key design principle of LH2 complexes: the Car triplet energy must be significantly lower than the BChl triplet energy to efficiently quench BChl triplets that otherwise act as potent “trap states,” causing exciton annihilation in laser-based experiments or photodamage in native membranes.
Absorption↗
Comparison of the Energy-Transfer Rates in Structural and Spectral Variants of the B800–850 Complex from Purple Bacteria
Photosynthetic light harvesting can occur with a remarkable near-unity quantum efficiency. The B800–850 complex, also known as light-harvesting complex 2 (LH2), is the primary light-harvesting complex in purple bacteria and has been extensively studied as a model system. The bacteriochlorophylls of the B800–850 complex are organized into two concentric rings, known as the B800 and B850 rings. However, depending on the species and growth conditions, the number of constituent subunits, the pigment geometry, and the absorption energies vary. While the dynamics of some B800–850 variants have been exhaustively characterized, others have not been measured. Furthermore, a direct and simultaneous comparison of how both structural and spectral differences between variants affect these dynamics has not been performed. In this work, we utilize ultrafast transient absorption measurements to compare the B800 to B850 energy-transfer rates in the B800–850 complex as a function of the number of subunits, geometry, and absorption energies. The nonameric B800–850 complex from Rhodobacter (Rb.) sphaeroides is 40% faster than the octameric B800–850 complex from Rhodospirillum (Rs.) molischianum, consistent with structure-based predictions. In contrast, the blue-shifted B800–820 complex from Rs. molischianum is only 20% faster than the B800–850 complex from Rs. molischianum despite an increase in the spectral overlap between the rings that would be expected to produce a larger increase in the energy-transfer rate. These measurements support current models that contain dark, higher-lying excitonic states to bridge the energy gap between rings, thereby maintaining similar energy-transfer dynamics. Altogether, these results demonstrate that energy-transfer dynamics in the B800–850 complex are robust to the spectral and structural variations between species used to optimize energy capture and flow in purple bacteria.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Charge Transfer and Recombination Pathways through Fullerene Guests in Porphyrin-Based MOFs
Porphyrin-based metal–organic frameworks (MOFs) offer a unique platform for building porous donor–acceptor networks that exhibit long-lived charge separation and transport upon incorporation of electron acceptor guest species. Here, in this work, porphyrin-based MOFs, PCN-222(H 2 ) and PCN-222(Zn), synthesized as nanoparticle suspensions, are successfully infiltrated with fullerene acceptor molecules, C 60 or PC 61 BM, in both polar and nonpolar solvent environments. The location and relative binding strength of these guest species are evaluated through a combination of N 2 physisorption measurements, photoluminescence quenching, and UV–vis absorption titration experiments. Semiempirical tight binding calculations are used to screen potential locations of the fullerene guest within the MOF pores, and hybrid density functional theory (DFT)-computed interaction energies confirm the energetically favorable positions. The fundamental photophysics of these donor–acceptor host–guest combinations are probed using ultrafast transient absorption spectroscopy. Sub-picosecond electron transfer involving initial exciplex population is observed, with slow charge recombination lifetimes on the order of τ ~1 ns for all systems in both dimethylformamide and 1,4-dioxane. Charge recombination occurs through population of fullerene and/or framework porphyrin triplet states depending on the porphyrin metalation status. The photophysics of the fullerene-loaded MOFs are discussed in the context of relevant porphyrin–fullerene donor–acceptor molecules to highlight the unique role of the framework environment in dictating photoinduced electron transfer and decay pathways.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Photoluminescent Cu(I) HETPHENs Featuring Bulky Alkyl-Substituted Phenanthrolines
Successful excited-state-enhancing substituent effect strategies applied in homoleptic Cu(I) metal-to-ligand charge transfer (MLCT) chromophores have been adapted to the heteroleptic phenanthroline (HETPHEN) platform, leveraging 2,9-mesityl-1,10-phenanthroline (mesPhen) in conjunction with a series of seven distinct 2,9- and 2,3,4,7,8,9-substituted phenanthrolines. The newly conceived CuHETPHEN complexes feature MLCT lifetimes ranging from 62 to 443 ns, all of which exhibit unprecedented room-temperature photoluminescence and demonstrate quantitative adherence to the energy gap law. TD-DFT calculations successfully modeled the systematic variation in electronic transition intensities, accounting for the experimentally observed UV–vis absorption bands across the entire series of molecules while providing detailed structural explanations for the variations in spectral profiles. These heteroleptic Cu(I) diimine chromophores exhibit thermally activated delayed fluorescence (TADF), with delayed fluorescence occurring between closely spaced 1 MLCT and 3 MLCT excited manifolds, having energetic separations of ΔE = 713–1009 cm –1 , as demonstrated here for the first time. Nanosecond and ultrafast transient absorption spectroscopy verified the MLCT nature of these excited states and extracted the time constants for the initial pseudo-Jahn–Teller distortion and intersystem crossing throughout the entire series of molecules. Lastly, the triplet photosensitization properties of these Cu(I) HETPHENs are demonstrated in a number of model photochemical transformations.
Chromophores↗
Ultrafast Jahn‐Teller Photoswitching in Cobalt Single‐Ion Magnets
Abstract Single‐ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and X‐ray emission spectroscopy are employed to track the photoinduced spin‐state switching of the prototypical complex [Co(terpy) 2 ] 2+ (terpy = 2,2′:6′,2″‐terpyridine) in solution phase. The combined measurements and their analysis supported by density functional theory (DFT), time‐dependent‐DFT (TD‐DFT) and multireference quantum chemistry calculations reveal that the complex undergoes a spin‐state transition from a tetragonally elongated doublet state to a tetragonally compressed quartet state on the femtosecond timescale, i.e., it sustains ultrafast Jahn‐Teller (JT) photoswitching between two different spin multiplicities. Adding new Co‐based complexes as possible contenders in the search for JT photoswitching SIMs will greatly widen the possibilities for implementing magnetic multifunctionality and eventually controlling ultrafast magnetization with optical photons.
36 MATERIALS SCIENCE↗