Synchrotron radiation is used to excite Ar to the intermediate states 3p 1/2 5 ͑3dЈ͓3 / 2͔ 1 , 5dЈ͓3 / 2͔ 1 , 5sЈ͓1 / 2͔ 1 , 7sЈ͓1 / 2͔ 1 ͒ and 3p 3/2 5 ͑6d͓1 / 2͔ 1 , 6d͓3 / 2͔ 1 , 8s͓3 / 2͔ 1 ͒, then excited by lasers to the autoionizing Rydberg series 3p 1/2 5 npЈ ͓͑1 / 2͔ 0,1 , ͓3 / 2͔ 1,2 ͒ and nfЈ͓5 / 2͔ 2. For the intermediate states of 5sЈ, 7sЈ, and 8s, the npЈ ͓͑1 / 2͔ 0 and ͓3 / 2͔ 2 ͒ series are observed with high intensity but not the npЈ ͓͑1 / 2͔ 1 and ͓3 / 2͔ 1 ͒ series when the polarization vectors of two light beams are in parallel; but when they are in orthogonal, the npЈ͓1 / 2͔ 0 series disappears, the npЈ͓3 / 2͔ 2 intensity remains, and the npЈ ͓͑1 / 2͔ 1 and ͓3 / 2͔ 1 ͒ series show up strongly. The intensity distribution of the npЈ series strongly depends on the intermediate state. The spectra of the npЈ series are assigned according to their intensity variation with the polarization vectors. The quantum defects determined for the series npЈ͓1 / 2͔ 0 ͑n =11-57͒, npЈ͓3 / 2͔ 2 ͑n =11-65͒, npЈ͓3 / 2͔ 1 ͑n =11-31͒, and nfЈ͓5 / 2͔ 2 ͑n =9-74͒ are 1.611Ϯ 0.011, 1.683Ϯ 0.013, 1.688Ϯ 0.010, and 0.016Ϯ 0.005, respectively. Our values are in excellent agreement with theoretical prediction. The spectral line shapes of autoionizing Rydberg states are analyzed with a Beutler-Fano profile. Reduced autoionization linewidths for the npЈ͓1 / 2͔ 0 ͑n =11-16͒ series vary in the range 2549-4145 cm −1 , and the nfЈ͓5 / 2͔ 2 ͑n =9-11͒ series in 186-247 cm −1 in reasonable agreement with theoretical prediction.

This work investigates the pyrolysis of n-butylbenzene, which widely exists in transportation fuels and their surrogate mixtures. Both reactive and stable pyrolysis products were comprehensively detected with synchrotron vacuum ultraviolet photoionization mass spectrometry. Their mole fractions versus temperature were also evaluated at 30, 150, and 760 Torr. A kinetic model of n-butylbenzene pyrolysis was developed, and new data were used to validate the model. On the basis of the modeling analysis, the benzylic C–C bond dissociation that forms the benzyl radical and the propyl radical was found to be a key decomposition reaction of n-butylbenzene at all investigated pressures, whereas H abstraction provided increasing contributions with increasing pressure. Compared with small alkylbenzenes, such as toluene and ethylbenzene, n-butylbenzene demonstrates different pyrolysis characteristics and chemistry because of the existence of its long alkyl side chain. n-Butylbenzene has a higher pyrolysis reactivity and lower decomposition temperature regions, which inhibit the further decomposition of the benzyl radical and the formation of highly unsaturated C2–C4 products. As a result, conventional combination reactions between aromatic radicals and highly unsaturated C2–C4 species are only minor formation pathways for indene and naphthalene in n-butylbenzene pyrolysis, while fuel-specific pathways become crucial instead. Furthermore, combination reactions involving the benzyl radical and the phenyl radical are crucial for the formation of many PAHs, especially phenanthrene and fluorene. The results in this work reveal the strong influence of side-chain length on the pyrolysis chemistry of alkylbenzenes and indicate a further need for exploring the influences of other structural features.

Allene and propyne as well as their cationic forms play important roles in combustion and interstellar chemistry and serve as a model system for molecular spectroscopic studies. Both cations show Jahn−Teller (J−T) distortions in their ground states. These J−T distortions make the theoretical and experimental studies of their electronic structures difficult. We produced allene cations upon electron bombardment during matrix deposition of Ar containing a small proportion of allene. The intensities of the absorption features of the allene cation decreased after irradiation with UV light, whereas new bands attributed to propyne cations increased. The observed line wavenumbers, relative intensities, and deuterium-substituted isotopic ratios of the isomers of C 3 H 4 + agree satisfactorily with those predicted by density functional theory at the B3PW91/ aug-cc-pVTZ level of theory. This method produced the hydrocarbon cations of interest with few other fragments that enabled the clear identification of the IR spectra of allene and propyne cations.

Glutathione (GSH), the most abundant nonenzymatic antioxidant in living systems, actively scavenges various exogenous/endogenous oxidizing species, defending important biomolecules against oxidative damages. Although it is well established that the antioxidant activity of GSH originates from the cysteinyl thiol (-SH) group, the molecular origin that makes the thiol group of GSH a stronger reducing agent than other thiol-containing proteins is unclear. To gain insights into the molecular basis underlying GSH's superior antioxidant capability, here we report, for the first time, the valence electronic structures of solvated GSH in the aqueous aerosol form via the aerosol vacuum ultraviolet photoelectron spectroscopy technique. The pH-dependent electronic evolution of GSH is obtained, and the possible correlations between GSH and its constituting amino acids are interrogated. The valence band maxima (VBMs) for GSH aqueous aerosols are found at 7.81, 7.61, 7.52, and 5.51 ± 0.10 eV at a pH of 1.00, 2.74, 7.00, and 12.00, respectively, which appear to be lower than the values of their corresponding hybrid counterparts collectively contributed from the three isolated constituting amino acids of GSH. An additional photoelectron feature is observed for GSH aqueous aerosols at pH = 12.00, where the thiol group on its Cys residue becomes deprotonated and the relatively well-separated feature allows its vertical ionization energy (VIE) to be determined as 6.70 ± 0.05 eV. Compared to a VIE of 6.97 ± 0.05 eV obtained for a similar thiolate feature observed previously for isolated Cys aqueous aerosols ( Su et al. VUV Photoelectron Spectroscopy of Cysteine Aqueous Aerosols: A Microscopic View of Its Nucleophilicity at Varying pH Conditions . J. Phys. Chem. Lett. 2015 , 6 , 817 - 823 ), a 0.27 eV reduction in the VIE is found for GSH, indicating that the outermost electron corresponding to the nonbonding electron on the thiolate group can be removed more readily from the GSH tripeptide than that from Cys alone. The possible origins underlying the decrease in the VBM of GSH with respect to that of each corresponding hybrid counterpart and the decrease in the VIE of the thiolate feature of GSH with respect to that of the isolated Cys are discussed, providing hints to understand the superior antioxidant capability of GSH from a molecular level.

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