Marco Reinhard
Associate Scientist, SLAC National Accelerator Laboratory
All Publications
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Solution phase high repetition rate laser pump x-ray probe picosecond hard x-ray spectroscopy at the Stanford Synchrotron Radiation Lightsource
STRUCTURAL DYNAMICS-US
2023; 10 (5): 054304
Abstract
We present a dedicated end-station for solution phase high repetition rate (MHz) picosecond hard x-ray spectroscopy at beamline 15-2 of the Stanford Synchrotron Radiation Lightsource. A high-power ultrafast ytterbium-doped fiber laser is used to photoexcite the samples at a repetition rate of 640 kHz, while the data acquisition operates at the 1.28 MHz repetition rate of the storage ring recording data in an alternating on-off mode. The time-resolved x-ray measurements are enabled via gating the x-ray detectors with the 20 mA/70 ps camshaft bunch of SPEAR3, a mode available during the routine operations of the Stanford Synchrotron Radiation Lightsource. As a benchmark study, aiming to demonstrate the advantageous capabilities of this end-station, we have conducted picosecond Fe K-edge x-ray absorption spectroscopy on aqueous [FeII(phen)3]2+, a prototypical spin crossover complex that undergoes light-induced excited spin state trapping forming an electronic excited state with a 0.6-0.7 ns lifetime. In addition, we report transient Fe Kβ main line and valence-to-core x-ray emission spectra, showing a unique detection sensitivity and an excellent agreement with model spectra and density functional theory calculations, respectively. Notably, the achieved signal-to-noise ratio, the overall performance, and the routine availability of the developed end-station have enabled a systematic time-resolved science program using the monochromatic beam at the Stanford Synchrotron Radiation Lightsource.
View details for DOI 10.1063/4.0000207
View details for Web of Science ID 001094050700002
View details for PubMedID 37901682
View details for PubMedCentralID PMC10613086
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Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy.
Nature communications
2023; 14 (1): 2443
Abstract
Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kβ main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kβ main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.
View details for DOI 10.1038/s41467-023-37922-x
View details for PubMedID 37147295
View details for PubMedCentralID 16604
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Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency.
The journal of physical chemistry letters
1800: 378-386
Abstract
Quantifying charge delocalization associated with short-lived photoexcited states of molecular complexes in solution remains experimentally challenging, requiring local element specific femtosecond experimental probes of time-evolving electron transfer. In this study, we quantify the evolving valence hole charge distribution in the photoexcited charge transfer state of a prototypical mixed valence bimetallic iron-ruthenium complex, [(CN)5FeIICNRuIII(NH3)5]-, in water by combining femtosecond X-ray spectroscopy measurements with time-dependent density functional theory calculations of the excited-state dynamics. We estimate the valence hole charge that accumulated at the Fe atom to be 0.6 ± 0.2, resulting from excited-state metal-to-metal charge transfer, on an 60 fs time scale. Our combined experimental and computational approach provides a spectroscopic ruler for quantifying excited-state valency in solvated complexes.
View details for DOI 10.1021/acs.jpclett.1c03613
View details for PubMedID 34985900
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Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO2 to CO
ACS CATALYSIS
2021; 11 (11): 6499-6509
View details for DOI 10.1021/acscatal.1c01157
View details for Web of Science ID 000661125100017
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Author Correction: Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer.
Nature chemistry
2021
View details for DOI 10.1038/s41557-021-00663-9
View details for PubMedID 33627886
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Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer.
Nature chemistry
2021
Abstract
It is well known that the solvent plays a critical role in ultrafast electron-transfer reactions. However, solvent reorganization occurs on multiple length scales, and selectively measuring short-range solute-solvent interactions at the atomic level with femtosecond time resolution remains a challenge. Here we report femtosecond X-ray scattering and emission measurements following photoinduced charge-transfer excitation in a mixed-valence bimetallic (FeiiRuiii) complex in water, and their interpretation using non-equilibrium molecular dynamics simulations. Combined experimental and computational analysis reveals that the charge-transfer excited state has a lifetime of 62fs and that coherent translational motions of the first solvation shell are coupled to the back electron transfer. Our molecular dynamics simulations identify that the observed coherent translational motions arise from hydrogen bonding changes between the solute and nearby water molecules upon photoexcitation, and have an amplitude of tenths of angstroms, 120-200cm-1 frequency and ~100fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer.
View details for DOI 10.1038/s41557-020-00629-3
View details for PubMedID 33589787
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Short-lived metal-centered excited state initiates iron-methionine photodissociation in ferrous cytochrome c.
Nature communications
2021; 12 (1): 1086
Abstract
The dynamics of photodissociation and recombination in heme proteins represent an archetypical photochemical reaction widely used to understand the interplay between chemical dynamics and reaction environment. We report a study of the photodissociation mechanism for the Fe(II)-S bond between the heme iron and methionine sulfur of ferrous cytochrome c. This bond dissociation is an essential step in the conversion of cytochrome c from an electron transfer protein to a peroxidase enzyme. We use ultrafast X-ray solution scattering to follow the dynamics of Fe(II)-S bond dissociation and 1s3p (Kbeta) X-ray emission spectroscopy to follow the dynamics of the iron charge and spin multiplicity during bond dissociation. From these measurements, we conclude that the formation of a triplet metal-centered excited state with anti-bonding Fe(II)-S interactions triggers the bond dissociation and precedes the formation of the metastable Fe high-spin quintet state.
View details for DOI 10.1038/s41467-021-21423-w
View details for PubMedID 33597529
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Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers
CHEMICAL SCIENCE
2020; 11 (17): 4360–73
View details for DOI 10.1039/c9sc06272f
View details for Web of Science ID 000532365500005
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Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers.
Chemical science
2020; 11 (17): 4360-4373
Abstract
Photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)4(2,2'-bipyridine)]2- (1), [Fe(CN)4(2,3-bis(2-pyridyl)pyrazine)]2- (2) and [Fe(CN)4(2,2'-bipyrimidine)]2- (3) were investigated in various solvents with static and time-resolved UV-Visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering (RIXS). This series of polypyridyl ligands, combined with the strong solvatochromism of the complexes, enables the 1MLCT vertical energy to be varied from 1.64 eV to 2.64 eV and the 3MLCT lifetime to range from 180 fs to 67 ps. The 3MLCT lifetimes in 1 and 2 decrease exponentially as the MLCT energy increases, consistent with electron transfer to the lowest energy triplet metal-centred (3MC) excited state, as established by the Tanabe-Sugano analysis of the Fe 2p3d RIXS data. In contrast, the 3MLCT lifetime in 3 changes non-monotonically with MLCT energy, exhibiting a maximum. This qualitatively distinct behaviour results from a competing 3MLCT → ground state (GS) electron transfer pathway that exhibits energy gap law behaviour. The 3MLCT → GS pathway involves nuclear tunnelling for the high-frequency polypyridyl breathing mode (hν = 1530 cm-1), which is most displaced for complex 3, making this pathway significantly more efficient. Our study demonstrates that the excited state relaxation mechanism of Fe polypyridyl photosensitizers can be readily tuned by ligand and solvent environment. Furthermore, our study reveals that extending charge transfer lifetimes requires control of the relative energies of the 3MLCT and the 3MC states and suppression of the intramolecular distortion of the acceptor ligand in the 3MLCT excited state.
View details for DOI 10.1039/c9sc06272f
View details for PubMedID 34122894
View details for PubMedCentralID PMC8159445
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Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering.
Nature communications
2020; 11 (1): 634
Abstract
The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip=2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kalpha and Kbeta X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. This 3MC state is populated with a 110fs time constant by 40% of the excited molecules while the rest relax to a 3MLCT excited state. The sensitivity of the Kalpha XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1s and 2p core-ionized states surfaces.
View details for DOI 10.1038/s41467-020-14468-w
View details for PubMedID 32005815
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Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy
Journal of Chemical Physics
2020; 152
View details for DOI 10.1063/1.5139441
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Excited state charge distribution and bond expansion of ferrous complexes observed with femtosecond valence-to-core x-ray emission spectroscopy.
The Journal of chemical physics
2020; 152 (7): 074203
Abstract
Valence-to-core x-ray emission spectroscopy (VtC XES) combines the sample flexibility and element specificity of hard x-rays with the chemical environment sensitivity of valence spectroscopy. We extend this technique to study geometric and electronic structural changes induced by photoexcitation in the femtosecond time domain via laser-pump, x-ray probe experiments using an x-ray free electron laser. The results of time-resolved VtC XES on a series of ferrous complexes [Fe(CN)2n(2, 2'-bipyridine)3-n]-2n+2, n = 1, 2, 3, are presented. Comparisons of spectra obtained from ground state density functional theory calculations reveal signatures of excited state bond length and oxidation state changes. An oxidation state change associated with a metal-to-ligand charge transfer state with a lifetime of less than 100 fs is observed, as well as bond length changes associated with metal-centered excited states with lifetimes of 13 ps and 250 ps.
View details for DOI 10.1063/1.5139441
View details for PubMedID 32087640
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Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy.
Chemical science
2019; 10 (22): 5749–60
Abstract
Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2'-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals.
View details for DOI 10.1039/c8sc04023k
View details for PubMedID 31293761
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Solvatochromic and Ligand Effects in Ultrafast Intramolecular Electron Transfer in Fe-based Molecular Photosensitizers
E D P SCIENCES. 2019
View details for DOI 10.1051/epjconf/201920509029
View details for Web of Science ID 000570451400193
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Resolving structures of transition metal complex reaction intermediates with femtosecond EXAFS.
Physical chemistry chemical physics : PCCP
2019
Abstract
Femtosecond-resolved Extended X-ray Absorption Fine Structure (EXAFS) measurements of solvated transition metal complexes are successfully implemented at the X-ray Free Electron Laser LCLS. Benchmark experiments on [Fe(terpy)2]2+ in solution show a signal-to-noise ratio on the order of 500, comparable to typical 100 ps-resolution synchrotron measurements. In the few femtoseconds after photoexcitation, we observe the EXAFS fingerprints of a short-lived (∼100 fs) intermediate as well as those of a vibrationally hot long-lived (∼ns) excited state.
View details for DOI 10.1039/c9cp03483h
View details for PubMedID 31441480
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Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy.
Angewandte Chemie (International ed. in English)
2019
Abstract
Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeII NHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3 MLCT state, from the initially excited 1 MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3 MC state, in competition with vibrational relaxation and cooling to the relaxed 3 MLCT state. The relaxed 3 MLCT state then decays much more slowly (7.6 ps) to the 3 MC state. The 3 MC state is rapidly (2.2 ps) deactivated to the ground state. The 5 MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3 MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.
View details for DOI 10.1002/anie.201908065
View details for PubMedID 31602726
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Probing the Electron Accepting Orbitals of Ni-Centered Hydrogen Evolution Catalysts with Noninnocent Ligands by Ni L-Edge and S K-Edge X-ray Absorption.
Inorganic chemistry
2018
Abstract
The valence electronic structure of several square planar Ni-centered complexes, previously shown to catalyze the hydrogen evolution reaction, are characterized using S K-edge and Ni L-edge X-ray absorption spectroscopy and electronic structure calculations. Measurement of the atomic Ni 3d and S 3p contributions enables assessment of the metal-ligand covalency of the electron accepting valence orbitals and yields insight into the ligand-dependent reaction mechanisms proposed for the catalysts. The electron accepting orbital of the Ni(abt)2 (abt = 2-aminobenzenethiolate) catalyst is found to have large ligand character (80%), with only 9% S 3p (per S) character, indicating delocalization over the entire abt ligand. Upon two proton-coupled reductions to form the Ni(abt-H)2 intermediate, the catalyst stores 1.8 electrons on the abt ligand, and the ligand N atoms are protonated, thus supporting its role as an electron and proton reservoir. The electron accepting orbitals of the Ni(abt-H)2 intermediate and Ni(mpo)2 (mpo = 2-mercaptopyridyl- N-oxide) catalyst are found to have considerably larger Ni 3d (46-47%) and S 3p (17-18% per S) character, consistent with an orbital localized on the metal-ligand bonds. This finding supports the possibility of metal-based chemistry, resulting in Ni-H bond formation for the reduced Ni(abt-H)2 intermediate and Ni(mpo)2 catalyst, a critical reaction intermediate in H2 generation.
View details for PubMedID 30351073
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Coherent structural dynamics observed with femtosecond Fe K alpha and K beta X-ray emission spectroscopies
AMER CHEMICAL SOC. 2018
View details for Web of Science ID 000447609103560
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Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2 '-bipyridine)(CN)(4)](2-)
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
2018; 20 (6): 4238–49
Abstract
The excited state dynamics of solvated [Fe(bpy)(CN)4]2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer (MLCT) excited state of [Fe(bpy)(CN)4]2- has a 19 picosecond lifetime and no discernable contribution from metal centered (MC) states in weak Lewis acid solvents, such as dimethyl sulfoxide and acetonitrile.1,2 In the present work, we use the same combination of spectroscopic techniques to measure the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)4]2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state has triplet (3MC) character, unlike other reported six-coordinate Fe(ii)-centered coordination compounds, which form MC quintet (5MC) states. The solvent dependent changes in excited state non-radiative relaxation for [Fe(bpy)(CN)4]2- allows us to infer the influence of the solvent on the electronic structure of the complex. Furthermore, the robust characterization of the dynamics and optical spectral signatures of the isolated 3MC intermediate provides a strong foundation for identifying 3MC intermediates in the electronic excited state relaxation mechanisms of similar Fe-centered systems being developed for solar applications.
View details for PubMedID 29364300
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Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy
SCIENCE
2017; 356 (6344): 1276-+
Abstract
The multifunctional protein cytochrome c (cyt c) plays key roles in electron transport and apoptosis, switching function by modulating bonding between a heme iron and the sulfur in a methionine residue. This Fe-S(Met) bond is too weak to persist in the absence of protein constraints. We ruptured the bond in ferrous cyt c using an optical laser pulse and monitored the bond reformation within the protein active site using ultrafast x-ray pulses from an x-ray free-electron laser, determining that the Fe-S(Met) bond enthalpy is ~4 kcal/mol stronger than in the absence of protein constraints. The 4 kcal/mol is comparable with calculations of stabilization effects in other systems, demonstrating how biological systems use an entatic state for modest yet accessible energetics to modulate chemical function.
View details for PubMedID 28642436
View details for PubMedCentralID PMC5706643
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photoaquation Mechanism of Hexacyanoferrate(II) Ions: Ultrafast 2D UV and Transient Visible and IR Spectroscopies
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2017; 139 (21): 7335–47
Abstract
Ferrous iron(II) hexacyanide in aqueous solutions is known to undergo photoionization and photoaquation reactions depending on the excitation wavelength. To investigate this wavelength dependence, we implemented ultrafast two-dimensional UV transient absorption spectroscopy, covering a range from 280 to 370 nm in both excitation and probing, along with UV pump/visible probe or time-resolved infrared (TRIR) transient absorption spectroscopy and density functional theory (DFT) calculations. As far as photoaquation is concerned, we find that excitation of the molecule leads to ultrafast intramolecular relaxation to the lowest triplet state of the [Fe(CN)6]4- complex, followed by its dissociation into CN- and [Fe(CN)5]3- fragments and partial geminate recombination, all within <0.5 ps. The subsequent time evolution is associated with the [Fe(CN)5]3- fragment going from a triplet square pyramidal geometry, to the lowest triplet trigonal bipyramidal state in 3-4 ps. This is the precursor to aquation, which occurs in ∼20 ps in H2O and D2O solutions, forming the [Fe(CN)5(H2O/D2O)]3- species, although some aquation also occurs during the 3-4 ps time scale. The aquated complex is observed to be stable up to the microsecond time scale. For excitation below 310 nm, the dominant channel is photooxidation with a minor aquation channel. The photoaquation reaction shows no excitation wavelength dependence up to 310 nm, that is, it reflects a Kasha Rule behavior. In contrast, the photooxidation yield increases with decreasing excitation wavelength. The various intermediates that appear in the TRIR experiments are identified with the help of DFT calculations. These results provide a clear example of the energy dependence of various reactive pathways and of the role of spin-states in the reactivity of metal complexes.
View details for DOI 10.1021/jacs.7b02769
View details for Web of Science ID 000402691800031
View details for PubMedID 28485597