High-resolution Absorption Spectroscopy Research Articles

Synthesis of an Insulated Oligo(phenylene ethynylene) Dimer Through Cyclodextrin-Based [c2]Daisy Chain Rotaxane

Oligo(phenylene ethynylene)s (OPEs) are π-conjugated systems with promising optical, bioactive, and electrical properties, making them valuable candidates for molecular electronics and biosensors. Controlling the arrangement and orientation of π-conjugated systems is crucial in developing molecular devices. Recently, we developed insulated diarylacetylene dimers using a [c2]daisy chain rotaxane strategy, which brings two cores into close proximity without covalent bonding and shields them with permethylated α-cyclodextrins. Here, we synthesized an insulated OPE dimer using a similar rotaxane strategy to investigate its optical properties. The rotaxane structure and optical properties were evaluated using nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization high-resolution mass spectrometry (ESI-HRMS), and absorption and fluorescence spectroscopy. This study is expected to contribute to the development of optical and electronic materials utilizing OPEs.

Porphyrin-based carbon dots as fluorescence probe for sensing of Fe3+ ion and S2- anion in aqueous solution

In this work, a facile bottom-up approach was employed to synthesize the porphyrin-citric acid-derived fluorescent carbon dots (Por-CA-CDs) using a single-step hydrothermal method. As-prepared Por-CA-CDs were well characterized using spectroscopic techniques such as FT-IR, high-resolution transmission electron microscopy, P-XRD, UV-Vis absorption, and photoluminescence spectroscopy. The synthesized Por-CA-CDs exhibited blue fluorescence with excellent photostability and diameter ranging from 2.4 to 6.4 nm. Por-CA-CDs show excitation-dependent emission behavior, with a quantum yield of 26% and were used for sensing of Fe3+ and S2− ions in an aqueous solution. Por-CA-CDs demonstrated a robust and selective reaction to Fe3+ compared to the other cations utilized in this investigation. The sensing capability of Por-CA-CDs with Fe3+ ions was evaluated with fluorescence spectroscopy, and results show a “Turn-Off” emission mode upon binding of Fe3+ with Por-CA-CDs. In metal ion sensing studies, the fluorescence intensity of Por-CA-CDs exhibited significant quenching upon the addition of Fe3+ at concentrations ranging from 0 to 230 μM, with a detection limit (LOD) of 3.2 × 10−8 M. The quenching efficiency and Stern-Volmer quenching constant were computed as 99.45% and 4.4 × 106 M−1, respectively. Interestingly, fluorescence of Por-CA-CDs can be regained with the addition of S2− (0-160 µM) with LOD of 4.3 × 10−6 M and Stern-Volmer quenching constant of 6 × 105 M−1. Most importantly, the toxicity assay revealed good reliability for samples in deionized, tap, and river water, suggesting applications for Fe3+ monitoring in complex environments.

Operando X-Ray Absorption Spectroscopy Characterization of Ir Catalyst Dynamics in a Realistic Proton Exchange Membrane Water Electrolyzer

Water electrolysis powered by renewable energy is a promising technology which can produce green H2 with no direct CO2 emissions. The US Department of Energy has set an ambitious target to bring down the cost of green H2 to $1 per kg within the next decade. To drive the innovation required to meet this target, it is essential we understand catalyst behavior in realistic zero gap membrane based electrolyzers operating at industrially relevant current densities. Towards this goal, we have developed methodologies for conducting high-resolution X-ray absorption spectroscopy at current densities of 2 A cm-2 in a synchrotron-compatible electrolyzer. This innovation enabled us to track dynamic changes in Ir oxidation during sustained operation of a realistic proton exchange membrane water electrolyzer (PEMWE). The hardware and techniques developed are also widely applicable to other types of electrolyzers and fuel cells.

Unraveling iron oxides as abiotic catalysts of organic phosphorus recycling in soil and sediment matrices

In biogeochemical phosphorus cycling, iron oxide minerals are acknowledged as strong adsorbents of inorganic and organic phosphorus. Dephosphorylation of organic phosphorus is attributed only to biological processes, but iron oxides could also catalyze this reaction. Evidence of this abiotic catalysis has relied on monitoring products in solution, thereby ignoring iron oxides as both catalysts and adsorbents. Here we apply high-resolution mass spectrometry and X-ray absorption spectroscopy to characterize dissolved and particulate phosphorus species, respectively. In soil and sediment samples reacted with ribonucleotides, we uncover the abiotic production of particulate inorganic phosphate associated specifically with iron oxides. Reactions of various organic phosphorus compounds with the different minerals identified in the environmental samples reveal up to twenty-fold greater catalytic reactivities with iron oxides than with silicate and aluminosilicate minerals. Importantly, accounting for inorganic phosphate both in solution and mineral-bound, the dephosphorylation rates of iron oxides were within reported enzymatic rates in soils. Our findings thus imply a missing abiotic axiom for organic phosphorus mineralization in phosphorus cycling.

The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors.

Sequential infiltration synthesis (SIS), also known as vapor phase infiltration (VPI), is a quickly expanding technique that allows growth of inorganic materials within polymers from vapor phase precursors. With an increasing materials library, which encompasses numerous organometallic precursors and polymer chemistries, and an expanding application space, the importance of understanding the mechanisms that govern SIS growth is ever increasing. In this work, we studied the growth of polycrystalline ZnO clusters and particles in three representative polymers: poly(methyl methacrylate), SU-8, and polymethacrolein using vapor phase diethyl zinc and water. Utilizing two atomic resolution methods, high-resolution scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, we probed the evolution of ZnO nanocrystals size and crystallinity level inside the polymers with advancing cycles─from early nucleation and growth after a single cycle, through the formation of nanometric particles within the films, and to the coalescence of the particles upon polymer removal and thermal treatment. Through in situ Fourier transform infrared spectroscopy and microgravimetry, we highlight the important role of water molecules throughout the process and the polymers' hygroscopic level that leads to the observed differences in growth patterns between the polymers, in terms of particle size, dispersity, and the evolution of crystalline order. These insights expand our understanding of crystalline materials growth within polymers and enable rational design of hybrid materials and polymer-templated inorganic nanostructures.

Operando double-edge high-resolution X-ray absorption spectroscopy study of BiVO4 photoanodes.

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed.

Fast and simple method for simultaneous determination of palladium and rhodium in spent automotive catalysts by high-resolution continuum source electrothermal atomic absorption spectroscopy

This work established a novel and fast method for the simultaneous determination of palladium and rhodium in spent automotive catalysts by high-resolution continuum source electrothermal atomic absorption spectroscopy (HR-CS ETAAS). For this purpose, a simple approach for the extraction of Pd and Rh from auto catalysts with aqua regia (HCl + HNO3 (3:1)) leaching was developed. The optimum conditions for leaching of both elements in an open system are 4 h, at 108 °C and a solid-to-liquid ratio of 1:40. Palladium and rhodium concentrations in obtained leachate were determined simultaneously in one firing using the less sensitive adjacent secondary lines for Pd at 360.955 nm (7.7% relative sensitivity) and for Rh at 361.251 nm (2.2% relative sensitivity). The pyrolysis and atomization temperatures were 1200 °C and 2600 °C, respectively. Under these conditions, the limits of detection for Pd (0.19 mg kg−1) and Rh (0.48 mg kg−1) were relatively high but the sensitivity of the developed method corresponds to common concentrations of the elements in spent automotive catalysts. The repeatability of the method expressed as a relative standard deviation was typically 10% for Pd and 7% for Rh.The trueness of the method was confirmed by analysis of the certified reference material – spent automobile catalyst (ERM EB 504). The recoveries of Pd and Rh from the spent automobile catalyst were 96.9%, and 87.9%, respectively. The method was successfully applied to the simultaneous determination of Pd and Rh in spent automotive catalysts without preliminary chemical separation.

Transient IR spectroscopy of optically centrifuged CO2 (R186-R282) and collision dynamics for the J = 244-282 states.

Collisions of optically centrifuged CO2 molecules with J = 244-282 (Erot = 22 800-30 300 cm-1) are investigated with high-resolution transient IR absorption spectroscopy to reveal collisional and orientational phenomena of molecules with hyper-thermal rotational energies. The optical centrifuge is a non-resonant optical excitation technique that uses ultrafast, 800 nm chirped pulses to drive molecules to extreme rotational states through sequential Raman transitions. The extent of rotational excitation is controlled by tuning the optical bandwidth of the excitation pulses. Frequencies of 30 R-branch ν3 fundamental IR probe transitions are measured for the J = 186-282 states of CO2, expanding beyond previously reported IR transitions up to J = 128. The optically centrifuged molecules have oriented angular momentum and unidirectional rotation. Polarization-sensitive transient IR absorption of individual rotational states of optically centrifuged molecules and their collision products reveals information about collisional energy transfer, relaxation kinetics, and dynamics of rotation-to-translation energy transfer. The transient IR probe also measures the extent of polarization anisotropy. Rotational energy transfer for lower energy molecules is discussed in terms of statistical models and a comparison highlights the role of increasing energy gap with J and angular momentum of the optically centrifuged molecules.

High-Resolution X-ray Absorption and Emission Spectroscopy for Detailed Analysis of New CO2 Methanation Catalysts.

A new approach for the characterization of CO2 methanation catalysts prepared by thermal decomposition of a nickel MOF by hard X-ray photon-in/photon-out spectroscopy in form of high energy resolution fluorescence detected X-ray absorption near edge structure spectroscopy (HERFD-XANES) and valence-to-core X-ray emission (VtC-XES) is presented. In contrast to conventional X-ray absorption spectroscopy, the increased resolution of both methods allows a more precise phase determination of the final catalyst, which is influenced by the conditions during MOF decomposition.

High-resolution absorption spectroscopy of room-temperature and jet-cooled ammonia between 59,000 and 93,000 cm−1

We present new high-resolution photoabsorption spectra of ammonia spanning the region between 59,000 cm−1 and 93,000 cm−1 that were recorded by using the Fourier Transform Spectrometer at the Synchrotron SOLEIL. This region extends from just above the Franck-Condon envelope for the Ã1A2″ ← X̃1A1′ transition to well above the NH3+X̃+2A2″ ionization threshold. The spectra were recorded at a measured resolution of 0.23 cm−1 in both a room-temperature cell (293 K) and in a slit-jet supersonic expansion (∼70 K). The absolute photoabsorption cross section with an uncertainty of ± 5% is also reported for the room-temperature spectrum. The present resolution is a factor of 10 – 100 times higher than in other recently reported broad band spectra of ammonia, and many of the observed bands show partially resolved rotational structure. We have attempted to assign this structure for a number of these bands. The oscillator strengths extracted from the data are in good agreement with previous measurements but, in the case of structured bands, the present higher resolution measurements return higher peak absorption cross sections, that increase further when the sample is cooled. The present higher resolution spectra suggest that a number of previous vibronic band assignments that were based on quantum defect considerations may require some revision. Finally, we discuss the substantial differences between the photoabsorption and photoionization data just above the first ionization threshold.

In-Situ Analysis of Corrosion Products in Molten Salt: X-ray Absorption Reveals Both Ionic and Metallic Species.

Understanding and controlling the chemical processes between molten salts and alloys is vital for the safe operation of molten-salt nuclear reactors. Corrosion processes in molten salts are highly dependent on the redox potential of the solution that changes with the presence of fission and corrosion processes, and as such, reactor designers develop electrochemical methods to monitor the salt. However, electrochemical techniques rely on the deconvolution of broad peaks, a process that may be imprecise in the presence of multiple species that emerge during reactor operation. Here, we describe in situ measurements of the concentration and chemical state of corrosion products in molten FLiNaK (eutectic mixture of LiF-NaK-KF) by high-resolution X-ray absorption spectroscopy. We placed a NiCr foil in molten FLiNaK and found the presence of both Ni2+ ions and metallic Ni in the melt, which we attribute to the foil disintegration due to Cr dealloying.

Measurement of Doppler effects in a cryogenic buffer-gas cell

Buffer-gas cooling is a universal cooling technique for molecules and used for various purposes. One of its applications is using molecules inside a buffer-gas cell for low-temperature spectroscopy. Although a high-intensity signal is expected in the cell, complex molecular dynamics is a drawback for precise spectroscopy. In this study, we performed high-resolution absorption spectroscopy of low-J transitions in the $\tilde{A}^2\Pi (0,0,0)-\tilde{X}^2\Sigma ^+(0,0,0)$ band of calcium monohydroxide (CaOH). CaOH molecules were produced by laser ablation in a copper cell and cooled to $\sim$5\,K using helium buffer gas. We probed the Doppler effects in a buffer-gas cell by injecting counter-propagating lasers inside the cell. The time evolutions of the Doppler width and shift were simulated using a dedicated Monte Carlo simulation and compared with data.

Comparison of excitation and kinetic temperatures in a laser-produced plasma using absorption spectroscopy.

High-resolution tunable laser absorption spectroscopy is used to measure time-resolved absorption spectra for six neutral uranium transitions in a laser-produced plasma. Analysis of the spectra shows that kinetic temperatures are similar for all six transitions, but excitation temperatures are higher than kinetic temperatures from 10-100 μs, indicating departures from local thermodynamic equilibrium.

Temperature dependence of the band gap of Si28 :P at very low temperatures measured via time-resolved optical spectroscopy

We measure the temperature dependence of the indirect band gap of isotopically purified $^{28}\mathrm{Si}$:P in the regime from 0.1 K to 3 K by high-resolution absorption spectroscopy of the donor bound exciton transition. The measurements increase the up-to-date precision of the temperature-dependent band gap change by more than one order of magnitude and reveal a ${\mathrm{T}}^{4}$ dependence which is about a factor of two less than observed in previous measurements. Such a ${\mathrm{T}}^{4}$ dependence is predicted by theory, but the absolute values differ between our experiment and the most up-to-date calculations by a factor of 30, corroborating that the electron-phonon interaction at low temperatures is still not correctly included into theory. What is more, the ability of such very high-precision band-gap measurements facilitates the use of time- and spatially resolved $^{28}\mathrm{Si}$:P absorption as a contactless, local thermometer and electric field sensor with a demonstrated time resolution of milliseconds.

Terahertz absorption spectroscopy for measuring atomic oxygen densities in plasmas

This paper describes the first implementation of terahertz (THz) quantum cascade lasers for high-resolution absorption spectroscopy on plasmas. Absolute densities of ground state atomic oxygen were directly obtained by using the fine structure transition at approximately 4.75 THz. Measurements were performed on a low-pressure capacitively coupled radio frequency oxygen discharge. The detection limit in this arrangement was found to be cm−3, while the measurement accuracy was within 5%, as demonstrated by reference measurements of a well-defined ammonia transition. The results show that the presented method is well suited to measure atomic oxygen densities, and it closes the THz gap for quantitative atomic density measurements in harsh environments such as plasmas.

Terahertz quantum-cascade lasers for high-resolution absorption spectroscopy of atoms and ions in plasmas

We report on terahertz (THz) quantum-cascade lasers (QCLs) based on GaAs/AlAs heterostructures, which exhibit single-mode emission at 3.360, 3.921, and 4.745 THz. These frequencies are in close correspondence to fine-structure transitions of Al atoms, N+ ions, and O atoms, respectively. Due to the low electrical pump power of these THz QCLs, they can be operated in a mechanical cryocooler in continuous-wave mode, while a sufficient intrinsic tuning range of more than 5 GHz is maintained. The single-mode operation and the intrinsic tuning range of these THz QCLs allow for the application of these lasers as radiation sources for high-resolution absorption spectroscopy to determine the absolute densities of Al atoms, N+ ions, and O atoms in plasmas.

High-resolution rovibrational spectroscopy of trans-formic acid in the v1 OH stretching fundamental: Dark state coupling and evidence for charge delocalization dynamics

High-resolution infrared (IR) reduced-Doppler absorption spectra of jet-cooled gas phase trans-formic acid in the v1 OH stretching fundamental region are reported for the first time, obtained by supersonically expanding trans-formic acid/Ar mixtures through a slit jet nozzle source and rotationally cooling to Trot ≈ 10.9(5) K, with absorption signals recorded by high-resolution difference-frequency IR absorption spectroscopy. Two a/b-type rovibrational bands of comparable intensity, one ∼10-fold weaker b-type band, and one ∼6-fold weaker a-type band are observed, with vibrational band origins at 3570.493(5), 3566.793(5), 3560.032(9), and 3534.6869(2) cm−1, respectively. Based on previous Raman jet spectroscopic work by Nejad and Sibert [A. Nejad, E.L. Sibert III, The Raman jet spectrum of trans-formic acid and its deuterated isotopologs: Combining theory and experiment to extend the vibrational database, J. Chem. Phys. 154(6) (2021) 064301.], these four rovibrational bands have been assigned to v1, (v2 + v7), (v6 + 2v7 + 2v9), and 2v3, respectively. Specifically, two of the three upper dark states (2171 (a′) and 617292 (a′)) are close enough to the “bright” 11 (a′) state to facilitate strong anharmonic resonance interactions, which results in intensity mixing into the two zero-order bands that would otherwise be “dark”. Furthermore, our high-resolution spectral analysis reveals that there are local rotational crossings between these zero-order 11 and 2171 states resulting in extra lines (i.e., some upper levels in the nominally v1 band have majority zero-order 2171 state character). This motivates development of a 3 coupled state (11, 2171, and 617292) picture to aid in the spectral analysis, which is able to match all 3 observed band origins and relative band intensities, as well as indicate the necessity of multistate (> 2) coupling. Though limited by range of J and Ka levels (J' ≤ 9 and Ka' ≤ 3) populated at supersonic jet temperatures, this work offers first precision spectroscopic analysis of trans-formic acid in the v1 OH stretch region, which should aid in assignment of the more complete yet highly congested room temperature FTIR spectra [D. Hurtmans, F. Herregodts, M. Herman, J. Liévin, A. Campargue, A. Garnache, A. Kachanov, Spectroscopic and ab initio investigation of the νOH overtone excitation in trans-formic acid, J. Chem. Phys. 113(4) (2000) 1535–1545.]. Finally, and in sharp contrast to the spectral complexity in the three predominantly b-type bands, the lone a-type 2v3 rovibrational band at 3534.6869(2) cm−1 is well described by a simple, rigid asymmetric top Hamiltonian.

Experimental and Theoretical Investigation of High-Resolution X-ray Absorption Spectroscopy (HR-XAS) at the Cu K-Edge for Cu2ZnSnSe4

Energy sustainability is critical for social activities in the human world. The quaternary compound Cu2ZnSnSe4 (CZTSe), as a promising candidate for thin-film solar cell absorption with medium-level thermoelectric performance, is of interest for the purpose of utilizing solar energy. The defect chemistry and atomic ordering in this particular compound also triggers interests in understanding its crystallographic structure as well as defects. Hereby, high energy resolution X-ray absorption spectroscopy is employed to investigate the electronic and geometric structural complexity in pristine and cobalt-doped Cu2ZnSnSe4. The occupational atomic sites of Cu are found to be mixed with the Zn atoms, forming CuZn anti-defects, which serve as a knob to tune local electronic structures. With proper doping, the band structure can be manipulated to improve the optical and thermoelectric properties of the CZTSe compounds.

Jahn-Teller effects in initial and final states: high-resolution X-ray absorption, photoelectron and Auger spectroscopy of allene.

Carbon K-edge resonant Auger spectra of gas-phase allene following excitation of the pre-edge 1s → π* transitions are presented and analysed with the support of EOM-CCSD/cc-pVTZ calculations. X-Ray absorption (XAS), X-ray photoelectron (XPS), valence band and non-resonant Auger spectra are also reanalysed with a series of computational approaches. The results presented demonstrate the importance of including nuclear ensemble effects for simulating X-ray observables and as an effective strategy for capturing Jahn-Teller effects in spectra.

Broadband soft X-ray source from a clustered gas target dedicated to high-resolution XCT and X-ray absorption spectroscopy.

The development of the broad-bandwidth photon sources emitting in the soft X-ray range has attracted great attention for a long time due to the possible applications in high-resolution spectroscopy, nano-metrology, and material sciences. A high photon flux accompanied by a broad, smooth spectrum is favored for the applications such as near-edge X-ray absorption fine structure (NEXAFS), extended X-ray absorption fine structure (EXAFS), or XUV/X-ray coherence tomography (XCT). So far, either large-scale facilities or technologically challenging systems providing only limited photon flux in a single shot dominate the suitable sources. Here, we present a soft, broad-band (1.5 nm - 10.7 nm) soft X-ray source. The source is based on the interaction of very intense laser pulses with a target formed by a cluster mixture. A photon yield of 2.4 × 1014 photons/pulse into 4π (full space) was achieved with a medium containing Xe clusters of moderate-size mixed with a substantial amount of extremely large ones. It is shown that such a cluster mixture enhances the photon yield in the soft X-ray range by roughly one order of magnitude. The size of the resulting source is not beneficial (≤500 µm but this deficit is compensated by a specific spectral structure of its emission fulfilling the specific needs of the spectroscopic (broad spectrum and high signal dynamics) and metrological applications (broad and smoothed spectrum enabling a sub-nanometer resolution limit for XCT).