In a multifaceted investigation combining local soft X-ray and vibrational spectroscopic probes with ab initio molecular dynamics simulations, hydrogen-bonding interactions of two key principal amine compounds in aqueous solution, ammonia (NH) and ammonium ion (NH), are quantitatively assessed in terms of electronic structure, solvation structure, and dynamics. From the X-ray measurements and complementary determination of the IR-active hydrogen stretching and bending modes of NH and NH in aqueous solution, the picture emerges of a comparatively strongly hydrogen-bonded NH ion via N-H donating interactions, whereas NH has a strongly accepting hydrogen bond with one water molecule at the nitrogen lone pair but only weakly N-H donating hydrogen bonds. In contrast to the case of hydrogen bonding among solvent water molecules, we find that energy mismatch between occupied orbitals of both the solutes NH and NH and the surrounding water prevents strong mixing between orbitals upon hydrogen bonding and, thus, inhibits substantial charge transfer between solute and solvent. A close inspection of the calculated unoccupied molecular orbitals, in conjunction with experimentally measured N K-edge absorption spectra, reveals the different nature of the electronic structural effects of these two key principal amine compounds imposed by hydrogen bonding to water, where a pH-dependent excitation energy appears to be an intrinsic property. These results provide a benchmark for hydrogen bonding of other nitrogen-containing acids and bases.
We present a liquid flatjet system for solution phase soft-x-ray spectroscopy. The flatjet set-up utilises the phenomenon of formation of stable liquid sheets upon collision of two identical laminar jets. Colliding the two single water jets, coming out of the nozzles with 50 μm orifices, under an impact angle of 48° leads to double sheet formation, of which the first sheet is 4.6 mm long and 1.0 mm wide. The liquid flatjet operates fully functional under vacuum conditions (<10−3 mbar), allowing soft-x-ray spectroscopy of aqueous solutions in transmission mode. We analyse the liquid water flatjet thickness under atmospheric pressure using interferomeric or mid-infrared transmission measurements and under vacuum conditions by measuring the absorbance of the O K-edge of water in transmission, and comparing our results with previously published data obtained with standing cells with Si3N4 membrane windows. The thickness of the first liquid sheet is found to vary between 1.4–3 μm, depending on the transverse and longitudinal position in the liquid sheet. We observe that the derived thickness is of similar magnitude under 1 bar and under vacuum conditions. A catcher unit facilitates the recycling of the solutions, allowing measurements on small sample volumes (∼10 ml). We demonstrate the applicability of this approach by presenting measurements on the N K-edge of aqueous NH4+. Our results suggest the high potential of using liquid flatjets in steady-state and time-resolved studies in the soft-x-ray regime.
The relaxation dynamics of the indoline dye D149, a well-known sensitizer for photoelectrochemical solar cells, have been extensively characterized in various organic solvents by combining results from ultrafast pump-supercontinuum probe (PSCP) spectroscopy, transient UV-pump VIS-probe spectroscopy, time-correlated single-photon counting (TCSPC) measurements as well as steady-state absorption and fluorescence. In the steady-state spectra, the position of the absorption maximum shows only a weak solvent dependence, whereas the fluorescence Stokes shift Dñ F correlates with solvent polarity. Photoexcitation at around 480 nm provides access to the S 1 state of D149 which exhibits solvation dynamics on characteristic timescales, as monitored by a red-shift of the stimulated emission and spectral development of the excited-state absorption in the transient PSCP spectra. In all cases, the spectral dynamics can be modeled by a global kinetic analysis using a time-dependent S 1 spectrum. The lifetime t 1 of the S 1 state roughly correlates with polarity [acetonitrile (280 ps) o acetone (540 ps) o THF (720 ps) o chloroform (800 ps)], yet in alcohols it is much shorter [methanol (99 ps) o ethanol (178 ps) o acetonitrile (280 ps)], suggesting an appreciable influence of hydrogen bonding on the dynamics. A minor component with a characteristic time constant in the range 19-30 ps, readily observed in the PSCP spectra of D149 in acetonitrile and THF, is likely due to removal of vibrational excess energy from the S 1 state by collisions with solvent molecules. Additional weak fluorescence in the range 390-500 nm is observed upon excitation in the S 0 -S 2 band, which contains short-lived S 2 -S 0 emission of D149. Transient absorption signals after excitation at 377.5 nm yield an additional time constant in the subpicosecond range, representing the lifetime of the S 2 state. S 2 excitation also produces photoproducts.
The 3d transition metals play a pivotal role in many charge transfer processes in catalysis and biology. X-ray absorption spectroscopy at the L-edge of metal sites probes metal 2p-3d excitations, providing key access to their valence electronic structure, which is crucial for understanding these processes. We report L-edge absorption spectra of Mn(acac) and Mn(acac) complexes in solution, utilizing a liquid flatjet for X-ray absorption spectroscopy in transmission mode. With this, we derive absolute absorption cross-sections for the L-edge transitions with peak magnitudes as large as 12 and 9 Mb for Mn(acac) and Mn(acac), respectively. We provide insight into the electronic structure with ab initio restricted active space calculations of these L-edge transitions, reproducing the experimental spectra with excellent agreement in terms of shapes, relative energies, and relative intensities for the two complexes. Crystal field multiplet theory is used to assign spectral features in terms of the electronic structure. Comparison to charge transfer multiplet calculations reveals the importance of charge transfer in the core-excited final states. On the basis of our experimental observations, we extrapolate the feasibility of 3d transition metal L-edge absorption spectroscopy using the liquid flatjet approach in probing highly dilute biological solution samples and possible extensions to table-top soft X-ray sources.
We demonstrate the feasibility of soft X-ray absorption spectroscopy in the water window using a table-top laser-based approach with organic molecules and inorganic salts in aqueous solution. A high-order harmonic source delivers femtosecond pulses of short wavelength radiation in the photon energy range from 220 to 450 eV. We report static soft X-ray absorption measurements in transmission on the solvated compounds O=C(NH 2 ) 2 , CaCl 2 , and NaNO 3 using flatjet technology. We monitor the absorption of the molecular samples between the carbon (∼280 eV) and nitrogen (∼400 eV) K-edges and compare our results with previous measurements performed at the BESSYII facility. We discuss the roles of pulse stability and photon flux in the outcome of our experiments. Our work paves the way toward table-top femtosecond, solution-phase soft X-ray absorption spectroscopy in the water window.
Aqueous proton transport plays a key role in acid–base neutralization and energy transport through biological membranes and hydrogen fuel cells. Extensive experimental and theoretical studies have resulted in a highly detailed elucidation of one of the underlying microscopic mechanisms for aqueous excess proton transport, known as the von Grotthuss mechanism, involving different hydrated proton configurations with associated high fluxional structural dynamics. Hydroxide transport, with approximately 2-fold-lower bulk diffusion rates compared to those of excess protons, has received much less attention. We present femtosecond UV/IR pump–probe experiments and ab initio molecular dynamics simulations of different proton transport pathways of bifunctional photoacid 7-hydroxyquinoline (7HQ) in water/methanol mixtures. For 7HQ solvent-dependent photoacidity, free-energy–reactivity correlation behavior and quantum mechanics/molecular mechanics (QM/MM) trajectories point to a dominant OH – /CH 3 O – transport pathway for all water/methanol mixing ratios investigated. Our joint ultrafast infrared spectroscopic and ab initio molecular dynamics study provides conclusive evidence for the hydrolysis/methanolysis acid–base neutralization pathway, as formulated by Manfred Eigen half a century ago. Our findings on the distinctly different acid–base reactivities for aromatic hydroxyl and aromatic nitrogen functionalities suggest the usefulness of further exploration of these free-energy–reactivity correlations as a function of solvent polarity. Ultimately the determination of solvent-dependent acidities will contribute to a better understanding of proton-transport mechanisms at weakly polar surfaces and near polar or ionic regions in transmembrane proton pump proteins or hydrogen fuel cell materials.
The photophysics of 7-hydroxyquinoline (7HQ) in protic media results from an interplay of acid-base chemistry, prompted by the effects of photoacidity of the hydroxyl group and photobasicity of the nitrogen atom in the quinoline aromatic system. With ultrafast IR spectroscopic measurements, we follow the proton transfer dynamics of 7HQ in its four possible charged forms in methanol solution. Using deuterated methanol as solvent, we determine deuteron transfer rates from the neutral to the zwitterionic form to be 330 ps, those from the cationic form to the zwitterionic form to be 170 ps, and those from the anionic form to the zwitterionic form to be 600 ps. We compare the observed IR-active fingerprint marker patterns in the electronic ground state and the first electronically excited L-state with those calculated using density functional theory and time-dependent density functional theory, respectively, and find good correspondence between experimental and calculated transitions. The calculations provide insight into the nature of electronic excitation of these four different charged forms of 7HQ, suggesting the key role of electronic charge distribution changes upon electronic excitation of 7HQ and hydrogen bond changes at the donor hydroxyl and acceptor nitrogen moieties.
We use N K-edge absorption spectroscopy to explore the electronic structure of the amine group, one of the most prototypical chemical functionalities playing a key role in acid-base chemistry, electron donor-acceptor interactions, and nucleophilic substitution reactions. In this study, we focus on aliphatic amines and make use of the nitrogen 1s core electron excitations to elucidate the roles of N-H σ* and N-C σ* contributions in the unoccupied orbitals. We have measured N K-edge absorption spectra of the ethylamine bases Et NH ( x = 0...3; Et- = CH-) and the conjugate positively charged ethylammonium cation acids Et NH ( y = 0...4; Et- = CH-) dissolved in the protic solvents ethanol and water. Upon consecutive exchange of N-H for ethyl-groups, we observe a spectral shift, a systematic decrease of the N K-edge pre-edge peak, and a major contribution in the post-edge region for the ethylamine series. Instead, for the ethylammonium ions, the consecutive exchange of N-H for ethyl groups leads to an apparent reduction of pre-edge and post-edge intensities relative to the main-edge band, without significant frequency shifts. Building on findings from our previously reported study on aqueous ammonia and ammonium ions, we can rationalize these observations by comparing calculated N K-edge absorption spectra of free and hydrogen-bonded clusters. Hydrogen bonding interactions lead only to minor spectral effects in the ethylamine series, but have a large impact in the ethylammonium ion series. Visualization of the unoccupied molecular orbitals shows the consecutive change in molecular orbital character from N-H σ* to N-C σ* in these alkylamine/alkylammonium ion series. This can act as a benchmark for future studies on chemically more involved amine compounds.
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