UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH2S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

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.

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.

Light-Induced Radical Formation and Isomerization of an Aromatic Thiol in Solution Followed by Time-Resolved X-ray Absorption Spectroscopy at the Sulfur K-Edge.

We applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ∼70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemical reaction pathways and transient products of sulfur-containing molecules in solution.

Element-specific characterization of transient electronic structure of solvated Fe(II) complexes with time-resolved soft X-ray absorption spectroscopy.

Polypyridyl transition-metal complexes are an intriguing class of compounds due to the relatively facile chemical designs and variations in ligand-field strengths that allow for spin-state changes and hence electronic configurations in response to external perturbations such as pressure and light. Light-activated spin-conversion complexes have possible applications in a variety of molecular-based devices, and ultrafast excited-state evolution in these complexes is of fundamental interest for understanding of the origins of spin-state conversion in metal complexes. Knowledge of the interplay of structure and valence charge distributions is important to understand which degrees of freedom drive spin-conversion and which respond in a favorable (or unfavorable) manner. To track the response of the constituent components, various types of time-resolved X-ray probe methods have been utilized for a broad range of chemical and biological systems relevant to catalysis, solar energy conversions, and functional molecular devices. In particular, transient soft X-ray spectroscopy of solvated molecules can offer complementary information on the detailed electronic structures and valence charge distributions of photoinduced intermediate species: First-row transition-metal L-edges consist of 2p-3d transitions, which directly probe the unoccupied valence density of states and feature lifetime broadening in the range of 100 meV, making them sensitive spectral probes of metal-ligand interactions. In this Account, we present some of our recent progress in employing picosecond and femtosecond soft X-ray pulses from synchrotron sources to investigate element specific valence charge distributions and spin-state evolutions in Fe(II) polypyridyl complexes via core-level transitions. Our results on transient L-edge spectroscopy of Fe(II) complexes clearly show that the reduction in σ-donation is compensated by significant attenuation of π-backbonding upon spin-crossover. This underscores the important information contained in transient metal L-edge spectroscopy on changes in the 3d orbitals including oxidation states, orbital symmetries, and covalency, which largely define the chemistry of these complexes. In addition, ligand K-edge spectroscopy reveals the "ligand view" of the valence charge density by probing 1s-2p core-level transitions at the K-edge of light elements such as nitrogen, carbon, and oxygen. In the case of Fe(II) spin-conversion complexes, additional details of the metal-ligand interactions can be obtained by this type of X-ray spectroscopy. With new initiatives in and construction of X-ray free-electron laser sources, we expect time-resolved soft X-ray spectroscopy to pave a new way to study electronic and molecular dynamics of functional materials, thereby answering many interesting scientific questions in inorganic chemistry and material science.

Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO)5 and Its Parent Compound Mn2(CO)10.

We present a time-resolved X-ray spectroscopic study of the structural and electronic rearrangements of the photocatalyst Mn2(CO)10 upon photocleavage of the metal-metal bond. Our study of the manganese K-edge fine structure reveals details of both the molecular structure and valence charge distribution of the photodissociated radical product. Transient X-ray absorption spectra of the formation of the Mn(CO)5 radical demonstrate surprisingly small structural modifications between the parent molecule and the resulting two identical manganese monomers. Small modifications of the local valence charge distribution are decisive for the catalytic activity of the radical product. The spectral changes reflect altered hybridization of metal-3d, metal-4p, and ligand-2p orbitals, particularly loss of interligand interaction, accompanied by the necessary spin transition due to radical formation. The spectral changes in the manganese pre- and main-edge region are well-reproduced by time-dependent density functional theory and ab initio multiple scattering calculations.

Identifying the major intermediate species by combining time-resolved X-ray solution scattering and X-ray absorption spectroscopy.

Identifying the intermediate species along a reaction pathway is a first step towards a complete understanding of the reaction mechanism, but often this task is not trivial. There has been a strong on-going debate: which of the three intermediates, the CHI2 radical, the CHI2-I isomer, and the CHI2(+) ion, is the dominant intermediate species formed in the photolysis of iodoform (CHI3)? Herein, by combining time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TR-XAS), we present strong evidence that the CHI2 radical is dominantly formed from the photolysis of CHI3 in methanol at 267 nm within the available time resolution of the techniques (∼20 ps for TRXL and ∼100 ps for TR-XAS). The TRXL measurement, conducted using the time-slicing scheme, detected no CHI2-I isomer within our signal-to-noise ratio, indicating that, if formed, the CHI2-I isomer must be a minor intermediate. The TR-XAS transient spectra measured at the iodine L1 and L3 edges support the same conclusion. The present work demonstrates that the application of these two complementary time-resolved X-ray methods to the same system can provide a detailed understanding of the reaction mechanism.

Density functional theory assessment of molecular structures and energies of neutral and anionic Al(n) (n = 2-10) clusters.

We report the results of a benchmarking study on hybrid, hybrid-meta, long-range-corrected, meta-generalized gradient approximation (meta-GGA), and GGA density functional theory (DFT) methods for aluminum (Al) clusters. A range of DFT functionals, such as B3LYP, B1B95, PBE0, mPW1PW91, M06, M06-2X, ωB97X, ωB97XD, TPSSh, BLYP, PBE, mPWPW91, M06-L, and TPSS, have been used to optimize the molecular structures and calculate the vibrational frequencies and four energetic parameters for neutral and anionic Al(n) (n = 2-10) clusters. The performances of these functionals are assessed systematically by calculating the vertical ionization energy for neutral Al clusters and the vertical electron detachment energy for anionic Al clusters, along with the cohesive energy and dissociation energy. The results are compared with the available experimental and high-level ab initio calculated results. The calculated results showed that the PBE0 and mPW1PW91 functionals generally provide better results than the other functionals studied. TPSS can be a good choice for the calculations of very large Al clusters. On the other hand, the B3LYP, BLYP, and M06-L functionals are in poor agreement with the available experimental and theoretical results. The calculated results suggest that the hybrid DFT functionals like B3LYP do not always provide better performance than GGA functionals.

Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency.

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.

New Analytical Method for Measuring the Atomic Weight of Neon Using Gas Chromatography with a Thermal Conductivity Detector.

The atomic weights of neon (Ne) gases were measured by gas chromatography with a thermal conductivity detector (GC-TCD). High-purity neon gas was used as the carrier and sample gases in this study, which is different from typical GC analysis. The peak signals from the GC-TCD appear when the thermal conductivity between the sample and carrier gases is different. In most gaseous molecules, the thermal conductivity has been assumed to be the same if the chemical species is the same. However, the thermal conductivity of neon gases shows different values among several manufacturers, because the relative abundance of the 22Ne isotope, which is quite large (∼10% in atmospheric neon), varies due to the mass fractionation during air separation. We identified the atomic weights of seven neon gases. Additionally, the absolute isotope ratios of all neon gases were measured using a magnetic sector type gas/mass spectrometer. The atomic weights of the seven neon gases were compared with the results obtained from GC-TCD, and the results agreed with each other within the expanded uncertainty (k = 2).

Following Metal-to-Ligand Charge-Transfer Dynamics with Ligand and Spin Specificity Using Femtosecond Resonant Inelastic X-ray Scattering at the Nitrogen K-Edge.

We demonstrate for the case of photoexcited [Ru(2,2'-bipyridine)3]2+ how femtosecond resonant inelastic X-ray scattering (RIXS) at the ligand K-edge allows one to uniquely probe changes in the valence electronic structure following a metal-to-ligand charge-transfer (MLCT) excitation. Metal-ligand hybridization is probed by nitrogen-1s resonances providing information on both the electron-accepting ligand in the MLCT state and the hole density of the metal center. By comparing to spectrum calculations based on density functional theory, we are able to distinguish the electronic structure of the electron-accepting ligand and the other ligands and determine a temporal upper limit of (250 ± 40) fs for electron localization following the charge-transfer excitation. The spin of the localized electron is deduced from the selection rules of the RIXS process establishing new experimental capabilities for probing transient charge and spin densities.

Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer.

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 62 fs 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 ångströms, 120-200 cm-1 frequency and ~100 fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer.

Chemical control of competing electron transfer pathways in iron tetracyano-polypyridyl photosensitizers.

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.

Transient metal-centered states mediate isomerization of a photochromic ruthenium-sulfoxide complex.

Ultrafast isomerization reactions underpin many processes in (bio)chemical systems and molecular materials. Understanding the coupled evolution of atomic and molecular structure during isomerization is paramount for control and rational design in molecular science. Here we report transient X-ray absorption studies of the photo-induced linkage isomerization of a Ru-based photochromic molecule. X-ray spectra reveal the spin and valence charge of the Ru atom and provide experimental evidence that metal-centered excited states mediate isomerization. Complementary X-ray spectra of the functional ligand S atoms probe the nuclear structural rearrangements, highlighting the formation of two metal-centered states with different metal-ligand bonding. These results address an essential open question regarding the relative roles of transient charge-transfer and metal-centered states in mediating photoisomerization. Global temporal and spectral data analysis combined with time-dependent density functional theory reveals a complex mechanism for photoisomerization with atomic details of the transient molecular and electronic structure not accessible by other means.

Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths.

We present a joint experimental and computational study of the hexacyanoferrate aqueous complexes at equilibrium in the 250 meV to 7.15 keV regime. The experiments and the computations include the vibrational spectroscopy of the cyanide ligands, the valence electronic absorption spectra, and Fe 1s core hole spectra using element-specific-resonant X-ray absorption and emission techniques. Density functional theory-based quantum mechanics/molecular mechanics molecular dynamics simulations are performed to generate explicit solute-solvent configurations, which serve as inputs for the spectroscopy calculations of the experiments spanning the IR to X-ray wavelengths. The spectroscopy simulations are performed at the same level of theory across this large energy window, which allows for a systematic comparison of the effects of explicit solute-solvent interactions in the vibrational, valence electronic, and core-level spectra of hexacyanoferrate complexes in water. Although the spectroscopy of hexacyanoferrate complexes in solution has been the subject of several studies, most of the previous works have focused on a narrow energy window and have not accounted for explicit solute-solvent interactions in their spectroscopy simulations. In this work, we focus our analysis on identifying how the local solvation environment around the hexacyanoferrate complexes influences the intensity and line shape of specific spectroscopic features in the UV/vis, X-ray absorption, and valence-to-core X-ray emission spectra. The identification of these features and their relationship to solute-solvent interactions is important because hexacyanoferrate complexes serve as model systems for understanding the photochemistry and photophysics of a large class of Fe(II) and Fe(III) complexes in solution.

Time-Resolved X-ray Spectroscopy in the Water Window: Elucidating Transient Valence Charge Distributions in an Aqueous Fe(II) Complex.

Time-resolved nitrogen-1s spectroscopy in the X-ray water window is presented as a novel probe of metal-ligand interactions and transient states in nitrogen-containing organic compounds. New information on iron(II) polypyridyl complexes via nitrogen core-level transitions yields insight into the charge density of the photoinduced high-spin state by comparing experimental results with time-dependent density functional theory. In the transient high-spin state, the 3d electrons of the metal center are more delocalized over the nearest-neighbor nitrogen atoms despite increased bond lengths. Our findings point to a strong coupling of electronic states with charge-transfer character, facilitating the ultrafast intersystem crossing cascade in these systems. The study also highlights the importance of local charge density measures to complement chemical interaction concepts of charge donation and back-bonding with molecular orbital descriptions of states.

Tracking reaction dynamics in solution by pump-probe X-ray absorption spectroscopy and X-ray liquidography (solution scattering).

Characterization of transient molecular structures formed during chemical and biological processes is essential for understanding their mechanisms and functions. Over the last decade, time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TRXAS) have emerged as powerful techniques for molecular and electronic structural analysis of photoinduced reactions in the solution phase. Both techniques make use of a pump-probe scheme that consists of (1) an optical pump pulse to initiate a photoinduced process and (2) an X-ray probe pulse to monitor changes in the molecular structure as a function of time delay between pump and probe pulses. TRXL is sensitive to changes in the global molecular structure and therefore can be used to elucidate structural changes of reacting solute molecules as well as the collective response of solvent molecules. On the other hand, TRXAS can be used to probe changes in both local geometrical and electronic structures of specific X-ray-absorbing atoms due to the element-specific nature of core-level transitions. These techniques are complementary to each other and a combination of the two methods will enhance the capability of accurately obtaining structural changes induced by photoexcitation. Here we review the principles of TRXL and TRXAS and present recent application examples of the two methods for studying chemical and biological processes in solution. Furthermore, we briefly discuss the prospect of using X-ray free electron lasers for the two techniques, which will allow us to keep track of structural dynamics on femtosecond time scales in various solution-phase molecular reactions.

Synthesis and detailed spectroscopic characterization of various hydroxy-functionalized fluorescent chalcones: A combined experimental and theoretical study.

Four different bright yellow to orange hydroxy-substituted chalcones (i.e., 2',4-di-hydroxy (1), 2',3',4-trihydroxy (2), 2',3',4'-trihydroxy (3), and 2'-hydroxy-4-methoxy (4) chalcones) were synthesized and characterized by LC-MS, FT-IR, FT-Raman, and fluorescence spectroscopy and thermogravimetric analysis. UV-visible absorption spectroscopy was also used. The experimental (theoretical) bandgaps of 1, 2, 3, and 4 are 2.89 (2.90), 2.93 (2.95), 3.04 (3.09), and 3.01 (2.91) eV, respectively. The hydroxy-substituted chalcones exhibited strong dual emissions as a consequence of the locally excited states followed by internal charge transfer processes. The molecular structures, lowest energy transitions, vibrational frequencies, and spectroscopic information were calculated using density functional theory and time-dependent density functional theory methods at the B3LYP/6-31G(d,p) theoretical level. The experimental and theoretical data were compared and the relationship between them was briefly discussed.

Strong Spin-Orbit Coupling Facilitates C-H Activation in the Reactions of Os(+) with CH3F: Theoretical Investigations.

The relativistic effects are essential for a complete understanding of the reactions involving heavy transition metal cations with hydrocarbons. Despite this, spin-orbit coupling (SOC) along the reaction pathway is rarely considered. In this work, we demonstrate an unusual SOC on the chemical reactivity of a reaction of Os(+) with methyl fluoride (CH3F) using density functional theory (DFT), high-level ab initio, and spin-orbit multiconfigurational ab initio methods. With the inclusion of the SO effect in the relevant potential energy surfaces (PESs), C-H bond activation by an Os(+) cation occurs readily via almost barrierless (about 2 kcal/mol) PESs of the SO coupled ground state. In contrast, a substantial reaction barrier was observed for C-F bond activation. The calculated results are in line with recent systematic experimental findings for reactions of transition metal cations with CH3F. These results show that the SO effect can facilitate specific bond activation in chemical reactions associated with catalytic transition metal cations.

Ligand-field symmetry effects in Fe(II) polypyridyl compounds probed by transient X-ray absorption spectroscopy.

Ultrafast excited-state evolution in polypyridyl Fe(II) complexes is of fundamental interest for understanding the origins of the sub-ps spin-state changes that occur upon photoexcitation of this class of compounds as well as for the potential impact such ultrafast dynamics have on incorporation of these compounds in solar energy conversion schemes or switchable optical storage technologies. We have demonstrated that ground-state and, more importantly, ultrafast time-resolved X-ray absorption methods can offer unique insights into the interplay between electronic and geometric structure that underpins the photo-induced dynamics of this class of compounds. The present contribution examines in greater detail how the symmetry of the ligand field surrounding the metal ion can be probed using these X-ray techniques. In particular, we show that steady-state K-edge spectroscopy of the nearest-neighbour nitrogen atoms reveals the characteristic chemical environment of the respective ligands and suggests an interesting target for future charge-transfer femtosecond and attosecond spectroscopy in the X-ray water window.