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At least 1,081 records · Page 60

Robust Machine Learning Inference from X-ray Absorption Near Edge Spectra through Featurization

X-ray absorption spectroscopy (XAS) is a commonly employed technique for characterizing functional materials. In particular, X-ray absorption near edge spectra (XANES) encode local coordination and electronic information, and machine learning approaches to extract this information are of significant interest. To date, most ML approaches for XANES have primarily focused on using the raw spectral intensities as input, overlooking the potential benefits of incorporating spectral transformations and dimensionality reduction techniques into ML predictions. Here, in this work, we focused on systematically comparing the impact of different featurization methods on the performance of ML models for XAS analysis. We evaluated the classification and regression capabilities of these models on computed data sets and validated their performance on previously unseen experimental data sets. Our analysis revealed an intriguing discovery: the cumulative distribution function feature achieves both high prediction accuracy and exceptional transferability. This remarkably robust performance can be attributed to its tolerance to horizontal shifts in the spectra, which is crucial when validating models using experimental data. While this work exclusively focuses on XANES analysis, we anticipate that the methodology presented here will hold promise as a versatile asset to the broader spectroscopy community.

36 MATERIALS SCIENCE↗

Energy-Efficient CO 2 Capture from Flue Gas by Absorption with Amino Acids and Crystallization with a Bis-Iminoguanidine

In this work, we report a hybrid solvent/solid-state approach to CO 2 separation from flue gas, consisting of absorption with aqueous glycine or sarcosine amino acids, followed by crystallization of the bicarbonate salt of glyoxal-bis(iminoguanidine) (GBIG), and subsequent solid-state CO 2 release from the bicarbonate crystals. In this process, the GBIG bicarbonate crystallization regenerates the amino acid sorbent at ambient temperature, and the CO 2 is subsequently released by mild heating (120 °C) of the GBIG bicarbonate crystals, which results in quantitative regeneration of GBIG. The cyclic capacities measured from multiple absorption–regeneration cycles are in the range of 0.2–0.3 mol CO 2 /mol amino acid. The regeneration energy of this hybrid solvent/solid-state approach is 24% and 40% lower than the regeneration energy of benchmark industrial sorbents monoethanolamine and sodium glycinate, respectively. Lastly, as the amino acid sorbent is never heated in the hybrid process, its loss through evaporation or degradation is minimized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

How Does Metal Spin State Affect Electronic Communication in Mixed-Valence Dimers? Insights from Ultrafast Near-Infrared and Soft X-ray Transient Absorption Spectroscopy

Recent advancements in photocatalysis, photovoltaics, and quantum information science take advantage of electron spin, and determining how spin multiplicity affects electron transfer is key to understanding these phenomena. Here, in this study, we examine how metal spin state affects electronic communication in an organometallic mixed-valence dimer, ferrocenyl cobaltocenium ([Fe II Cp 2 Co III Cp 2 ] + ). This complex can be photoexcited from its low-spin singlet Fe II ground state to form intermediate-spin triplet Fe II and high-spin quintet Fe II excited states. Using femtosecond optical transient absorption (OTA) spectroscopy with visible (vis), near-infrared (NIR), and short-wave IR (SWIR) probes, supported by time-dependent density functional theory (TD-DFT) calculations, we measure Fe II Co III →Fe III Co II intervalence charge transfer (IVCT) bands in each of the Fe II spin states. Mulliken–Hush analysis of the excited-state IVCT bands was used to compute the electronic coupling between the metal centers in all three spin states, which increased as quintet < triplet < singlet. Meanwhile, the peak energy of the bands, and thus the ΔG of the IVCT transition, increased as triplet < quintet < singlet. Then, to directly probe the electronic structure at each metal center, we employed picosecond soft X-ray transient absorption (XTA) spectroscopy at the Fe and Co L 3 edges. Our results show that the low-spin and high-spin states of [Fe II Cp 2 Co III Cp 2 ] + are valence-localized, while the intermediate-spin state is partially delocalized. The differences in charge delocalization are attributed to differences in orbital occupation and geometry that affect the free energy and superexchange coupling.

Burke, John H. [Univ. of Illinois at Urbana-Champa↗

X-ray Absorption Spectroscopy and Theoretical Investigation of the Reductive Protonation of Cyclopentadienyl Cobalt Compounds

Cobalt(III) hydrides, formed via protonation of basic cobalt(I) centers, have long been recognized as key intermediates in the electrocatalytic reduction of protons to hydrogen. An understanding of the structural and electronic factors that govern their formation is key to developing more efficient and potent catalysts. A combination of Co K-edge X-ray absorption spectroscopy, extended X-ray absorption fine structure, density functional theory (DFT), and time-dependent DFT methods have been used to investigate several cyclopentadienyl (Cp) Co(III)L (L = ligand) species and their two-electron reduced Co(I) analogues. The results reveal that when L is strongly π-accepting, the reduced species demonstrates strong backbonding between the electron-rich Co(I) center and the ligand L, resulting in a weakly basic Co center that does not protonate to form a Co(III)–H. In contrast, a weakly π-accepting or σ-donating ligand system results in an electron-rich Co(I) center, which is readily protonated to form a Co(III)–H. Here, this study reveals the strength of a combined X-ray spectroscopy/theory method in understanding the role of ligands in tuning the electronic structure and subsequent reactivity of the metal center.

36 MATERIALS SCIENCE↗

X-ray Absorption Spectroscopy Investigations of Copper(II) Coordination in the Human Amyloid β Peptide

Alzheimer’s disease (AD) is the main cause of age-related dementia and currently affects approximately 5.7 million Americans. Major brain changes associated with AD pathology include accumulation of amyloid beta (Aβ) protein fragments and formation of extracellular amyloid plaques. Redox-active metals mediate oligomerization of Aβ, and the resultant metal-bound oligomers have been implicated in the putative formation of harmful, reactive species that could contribute to observed oxidative damage. In isolated plaque cores, Cu(II) is bound to Aβ via histidine residues. Despite numerous structural studies of Cu(II) binding to synthetic Aβ in vitro, there is still uncertainty surrounding Cu(II) coordination in Aβ. In this study, we used X-ray absorption spectroscopy (XAS) and high energy resolution fluorescence detected (HERFD) XAS to investigate Cu(II) coordination in Aβ(1–42) under various solution conditions. We found that the average coordination environment in Cu(II)Aβ(1–42) is sensitive to X-ray photoreduction, changes in buffer composition, peptide concentration, and solution pH. Fitting of the extended X-ray absorption fine structure (EXAFS) suggests Cu(II) is bound in a mixture of coordination environments in monomeric Aβ(1–42) under all conditions studied. However, it was evident that on average only a single histidine residue coordinates Cu(II) in monomeric Aβ(1–42) at pH 6.1, in addition to 3 other oxygen or nitrogen ligands. Here, Cu(II) coordination in Aβ(1–42) at pH 7.4 is similarly 4-coordinate with oxygen and nitrogen ligands, although an average of 2 histidine residues appear to coordinate at this pH. At pH 9.0, the average Cu(II) coordination environment in Aβ(1–42) appears to be 5-coordinate with oxygen and nitrogen ligands, including two histidine residues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two-Component Multireference Restricted Active Space Configuration Interaction for the Computation of L-Edge X-ray Absorption Spectra

X-ray absorption spectroscopy is a powerful probe of local electronic and nuclear structure, providing insights into chemical processes. The theoretical prediction and interpretation of metal L-edge X-ray absorption spectra is complicated by both relativistic effects, including spin-orbit coupling, and by the multiconfigurational nature of the states involved. This work details an exact two-component multireference restricted active space configuration interaction (X2C-MRRASCI) scheme that uses an exact two-component state average complete active space self-consistent-field method (X2C-SA-CASSCF), which includes the spin-orbit coupling in a variational manner, for the accurate description of the electronic structure before using a restricted active space configuration interaction method to describe the core excited states of the X-ray spectrum. Benchmark calculations are presented for a series of iron containing complexes, with results showing key features of the spectrum being reproduced, including ligand to metal charge transfer and shake-up excitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Data-Driven Recommendation of Optimal Tuning Scheme for Range-Separated Hybrid Functionals in Solution-Phase UV/Vis Absorption Energy Prediction

Time-dependent density functional theory (TDDFT) combined with range-separated hybrid (RSH) functionals and a tuned range-separation parameter γ offers a computationally economical approach for high-throughput excited- state property predictions. The γ-tuning procedure in the gas phase is well established. However, no agreement on the best γ- tuning procedure has been made when considering the solvent effect with implicit solvent models like the polarizable continuum model (PCM). To answer that question, this study created a diverse dataset with 937 molecules with experimental solutionphase UV/vis absorption spectra. Three γ-tuning methods, the gasphase γ-tuning (GPγT), the partial vertical γ-tuning (PVγT), and the strict vertical γ-tuning (SVγT), were evaluated for the ωPBEh functional over the entire dataset. Additional benchmarks are done for the optimally tuned screened range-separated hybrid combined with the PCM approach (SRSH-PCM) and the solvation-mediated tuning procedure (sol-med-OT). Our findings revealed that the optimal γ-values obtained by the PVγT and the SVγT are significantly smaller than the GPγT. This trend holds consistently across all molecules in our dataset, and we explained the origin of this phenomenon. TDDFT calculations with PVγTand SVγT-tuned γ-values and default global Fock exchange fraction achieve superior performance compared to those using GPγTtuned or default γ and slightly outperform SRSH-PCM and sol-med-OT with similar or lesser computational cost. Furthermore, we found that the smaller γ-values from SVγT captured the expected 1/(εR) asymptotic behavior in the solution phase, resulting in accurate prediction of solution-phase CT excitations, consistent with the screened asymptote behavior encoded in SRSH-PCM. These results show that SVγT is the best scheme for high-throughput UV/vis absorption spectrum calculations using the ωPBEh functional from a data-driven perspective.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CpHMD-Then-QM/MM Identification of the Amino Acids Responsible for the Anabaena Sensory Rhodopsin pH-Dependent Electronic Absorption Spectrum

Anabaena Sensory Rhodopsin (ASR), a microbial photoactive protein featuring the retinal chromophore in two different conformations, exhibits a pH-dependent electronic absorption spectrum. Using the recently developed CpHMD-then-QM/MM multiscale protocol applied to ASR embedded in a membrane model, the pH-induced changes in its maximum absorption wavelength have been reproduced and analyzed. While the acidic tiny red-shift is essentially correlated with the deprotonation of an aspartic acid located on the ASR extracellular side, the larger blue-shift experimentally reported at pH values larger than 5 involves a cluster of titrating residues sitting on the cytoplasmic side. The ASR pH-dependent spectrum is the consequence of the competitive stabilization of retinal ground and excited states by the protein electrostatic potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Role of Spin–Orbit Coupling in the Linear Absorption Spectrum and Intersystem Crossing Rate Coefficients of Ruthenium Polypyridyl Dyes

The successful use of molecular dyes for solar energy conversion requires efficient charge injection, which in turn requires the formation of states with sufficiently long lifetimes (e.g., triplets). The molecular structure elements that confer this property can be found empirically, however computational predictions using ab initio electronic structure methods are invaluable to identify structure-property relations for dye sensitizers. The primary challenge for simulations to elucidate the electronic and nuclear origins of these properties is a spin-orbit interaction which drives transitions between electronic states. Here, in this work, we present a computational analysis of the spin-orbit corrected linear absorption cross sections and intersystem crossing rate coefficients for a derivative set of phosphonated tris(2,2'-bipyridine)ruthenium(2+) dye molecules. After sampling the ground state vibrational distributions, the predicted linear absorption cross sections indicate that the mixture between singlet and triplet states plays a crucial role in defining the line shape of the metal-to-ligand charge transfer bands in these derivatives. Additionally, an analysis of the intersystem crossing rate coefficients suggests that transitions from the singlet into the triplet manifolds are ultrafast with rate coefficients on the order of 10 13 s -1 for each dye molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulating X-ray Absorption Spectra with Linear-Response Density Cumulant Theory

We present a new approach for simulating X-ray absorption spectra based on linear-response density cumulant theory (LR-DCT) [Copan, A. V.; Sokolov, A. Yu. J. Chem. Theory Comput. 2018, 14, 4097–4108]. Our new method combines the LR-ODC-12 formulation of LR-DCT with core- valence separation approximation (CVS) that allows us to efficiently access high-energy core-excited states. We describe our computer implementation of the CVS-approximated LRODC-12 method (CVS-ODC-12) and benchmark its performance by comparing simulated X-ray absorption spectra to those obtained from experiment for several small molecules. Our results demonstrate that the CVS-ODC-12 method shows good agreement with experiment for relative spacings between transitions and their intensities, but the excitation energies are systematically overestimated. When compared to results from excited-state coupled cluster methods with single and double excitations, the CVS-ODC-12 method shows a similar performance for intensities and peak separations, while coupled cluster spectra are less shifted, relative to experiment. An important advantage of CVS-ODC-12 is that its excitation energies are computed by diagonalizing a Hermitian matrix, which enables efficient computation of transition intensities.

Peng, Ruojing↗

Effect of Ions on the Optical Absorption Spectra of Aqueously Solvated Chromophores

In the condensed phase, ions often create heterogeneous local environments around a solute, which may impart chemical reactivity or perturbations to physico-chemical properties. Although the former has been the subject of some study, the latter - particularly as is pertains to optical absorption spectroscopy - is much less understood. As such, in this work, the computed UV-Vis absorption spectrum is examined for the aqueously solvated chromophore anion of green fluorescent protein for different local ion configurations. The strong ability of water to screen the ions from the chromophore results in little change in excitation energy compared to a purely aqueous environment. However, upon forming a contact ion pair with a sodium ion at either of the two electronegative oxygen sites of the chromophore, there is a spectral shift to either higher or lower energies. Surprisingly, our analysis suggests that the cause of the spectral shift is dominated not by the electrostatic presence of the ion, but instead by ion disruption of the hydrogen bond network at the oxygen contact ion pair site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvated Electron in Acetonitrile: Radiation Yield, Absorption Spectrum, and Equilibrium between Cavity- and Solvent-Localized States

The equilibrium between a solvent cavity-localized electron, ecav-, and a dimeric solvent anion, (CH 3 CN)$_{2}^{•-}$, which are the two lowest energy states of the solvated electron in acetonitrile, has been investigated by pulse radiolysis at 233-353 K. The enthalpy and entropy for the e$_{cav}^{-}$ to (CH 3 CN)$_{2}^{•-}$ conversion amount to -11.2 ± 0.3 kcal/mol and -39.3 ± 1.2 cal/(mol K), corresponding to a 0.44 ± 0.35 equilibrium constant at 25 °C. The radiation yield of the solvated electron has been quantified using a Co(II) macrocycle that scavenges electrons with a 1.55 × 10 11 M -1 s -1 rate constant. The apparent yield increases without saturation over the attainable scavenger concentration range, reaching 2.8 per 100 eV; this value represents the lower limit for the acetonitrile ionization yield in pulse radiolysis. The apparent molar absorption coefficient of (20.8 ± 1.5) × 10 3 M -1 cm -1 at 1450 nm and 20 °C for the solvated electron and individual vis-near-infrared (NIR) absorption spectra of e$_{cav}^{-}$ and (CH 3 CN)$_{2}^{•-}$ are derived from the data. Variances with previous reports are thoroughly discussed. All together, these results resolve several controversies concerning the solvated electron properties in acetonitrile and furnish requisite data for quantitative pulse radiolysis investigations in this commonly used solvent.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Molecular Origins of Temperature-Dependent X-ray Absorption in YAG:Dy

The absorption and emission of X-rays in dysprosium-doped yttrium aluminum garnet (YAG:Dy) has produced unexpected thermographic behavior, which is investigated using a combination of finite temperature ab initio molecular dynamic simulations, structural characterization, and electronic structure calculations of X-ray characteristics. Calculated average peak X-ray absorption spectra (XAS) from simulations between 300 and 600 K result in peak intensity loss due to thermalization effects, matching experimentally measured behavior of YAG:Dy. Here, investigation of atomic snapshots indicates structural factors that correlated with the X-ray behavior, with the first Y–O coordination sphere identified as the primary structural feature unique to high XAS intensity as calculated by radial and pair distribution functions.

Ab initio molecular dynamics↗

Physical Origins of the Transient Absorption Spectra and Dynamics in Thin-Film Semiconductors: The Case of BiVO 4

Transient absorption (TA) spectroscopy is uniquely suited for understanding kinetic processes initiated by light over vast ranges of time. In combination with white light probes, the recorded differential absorption spectra can contain spectroscopic signatures characteristic of specific charge carrier population densities. However, disentangling the often-complex and convoluted spectra is made challenging without robust analysis methods relating the underlying physical mechanisms to the spectral components. In this work, we address the origin of the transient spectra of a model system of emerging solar energy harvesting materials using a monoclinic BiVO 4 thin film. Using ground-state optical properties of the semiconductor, we find the main derivative-like spectral response to be related to shifting and broadening of oscillators, rather than specific carrier-related transitions. However, by using the Drude optical model of free carriers, we also identify the transient response related to free-hole density. Importantly, sample heating from the optical pumping, which begins at ~10 ps and plateaus by ~200 ps, dominates the overall spectral response at longer times. On the basis of a physical model of the spectral response, a kinetic model is developed that describes the pump power dependence of the free-hole density, as well as the temporal evolution of the spectral changes associated with shifting and broadening of oscillators. First-principles density functional theory calculations are used to rationalize experimental measurements. Here, this comprehensive approach to analyzing and modeling the TA spectra offers a generalizable basis for understanding the complex pump-probe data, reveals thermal heating artifacts that are frequently erroneously assigned to long-lived photocarriers, and offers a path to eliminating ambiguity in analysis of photocarrier dynamics in solid-state systems.

36 MATERIALS SCIENCE↗

Near-Quantitative Predictions of the First-Shell Coordination Structure of Hydrated First-Row Transition Metal Ions Using K-Edge X-ray Absorption Near-Edge Spectroscopy

Understanding the solvation structure of transition metal ions is important due to its broad impact on the kinetics, stability, and reactivity in a variety of applications in geochemistry, biochemistry, energy storage, and environmental chemistry. Using water as the common ligand, we study the X-ray absorption pre-edge and near-edge spectra at the K-edge of a near-complete series of hydrated first-row transition metal ions with d-orbital occupancy ranging from d 2 to d 10 . Starting with optimized structures that were derived from an explicit solvation treatment at the density functional theory (DFT) level, we then compute the pre-edge X-ray absorption spectra at the metal ion K-edge at the time dependent density functional theory (TDDFT) and restricted active-space second-order perturbation theory (RASPT2) levels of theory. TDDFT calculations provide accurate results for spectra that are dominated by single excitations, while significant improvements were obtained with RASPT2 calculations that correctly distinguish between singly and doubly excited states, where relevant, with quantitative accuracy compared with experiment. We analyze and assign the dierent pre-edge features for each metal ion in order to reveal the impact of the variations in the d orbital occupancy on the rst-shell coordination environment. For completeness, we also report the lowest energy ligand-field d-d transitions for all the transition metal aqua ions considered in this study using complete active space second order perturbation theory (CASPT2).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Combined Wave Function and Density Functional Approach for K-Edge X-ray Absorption Near-Edge Spectroscopy: A Case Study of Hydrated First-Row Transition Metal Ions

The prediction of X-ray absorption spectra (XAS) of transition metal complexes has important and broad application areas in chemistry and biology. In this letter, we have investigated the predictive ability of multiconfiguration pair-density functional theory (MC-PDFT) for X-ray absorption spectra by calculating the metal K pre-edge features of aquated 3d transition metal ions in common oxidation states. MC-PDFT results were compared with experimentally measured spectra as well as analyzed against results from restricted active-space second-order perturbation theory (RASPT2) and time-dependent density functional theory (TDDFT). As expected, TDDFT performs well for excited states that can be accurately represented by singly excited configurations but fails for excited states where higher order excitations become important. On the other hand, both RASPT2 and MC-PDFT provide quantitatively accurate results for all excited states irrespective of their character. While core-level spectroscopy with RASPT2 is accurate, it is computationally expensive. Finally, our results show that MC-PDFT performs equally well with significantly lower computational cost and is an encouraging alternate approach for X-ray spectroscopies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reaction Ensemble Monte Carlo Simulations of CO 2 Absorption in the Reactive Ionic Liquid Triethyl(octyl)phosphonium 2-Cyanopyrrolide

The absorption of CO 2 into an aprotic heterocyclic anion ionic liquid (IL) is modeled here using reaction ensemble Monte Carlo (RxMC) with the semigrand reaction move. RxMC has previously been unable to sample chemical equilibrium involving molecular ions in nanostructured liquids due to the high free-energy requirements to open and close cavities and restructure the surrounding environment. Our results are validated by experiments in the modeled IL, triethyl(octyl)phosphonium 2-cyanopyrrolide ([P 2228 ][cnp]), and in a close analog with longer alkyl chains on the cation. Heats of absorption and reaction from both experiment and simulation are exothermic and of comparable magnitude. Replacing experimental Henry’s constants with their simulated counterparts improves the accuracy of a Langmuir-type model at moderate pressures. Nonidealities that affect chemical equilibrium are identified and calculated with high precision.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stimulated X-ray Raman and Absorption Spectroscopy of Iron–Sulfur Dimers

Iron–sulfur complexes play an important role in biological processes such as metabolic electron transport. A detailed understanding of the mechanism of long-range electron transfer requires knowledge of the electronic structure of the complexes, which has traditionally been challenging to obtain, either by theory or by experiment, but the situation has begun to change with advances in quantum chemical methods and intense free electron laser light sources. We compute the spectra for stimulated X-ray Raman spectroscopy (SXRS) and absorption spectroscopy of homovalent and mixed-valence [2Fe–2S] complexes, using the ab initio density matrix renormalization group algorithm. The simulated spectra show clear signatures of the theoretically predicted dense low-lying excited states within the d–d manifold. Finally, the difference in spectral intensity between the absorption-active and Raman-active states provides a potential mechanism to selectively excite states by a proper tuning of the excitation pump, to access the electronic dynamics within this manifold.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗