Novel techniques in VUV high-resolution spectroscopy

Novel VUV sources and techniques for VUV spectroscopy are reviewed. Laser-based VUV sources have been developed via non-linear upconversion of laser pulses in the nanosecond (ns), the picosecond (ps), and femtosecond (fs) domain, and are applied in high-resolution gas phase spectroscopic studies. While the ns and ps pulsed laser sources, at Fourier-transform limited bandwidths, are used in wavelength scanning spectroscopy, the fs laser source is used in a two-pulse time delayed mode. In addition a Fourier-transform spectrometer for high resolution gas-phase spectroscopic studies in the VUV is described, exhibiting the multiplex advantage to measure many resonances simultaneously.Comment: 17 Pages, 8 figures, Conference proceedings of the VUV/X-ray 2013 at Hefei, Chin

The CO A-X System for Constraining Cosmological Drift of the Proton-Electron Mass Ratio

The $\textrm{A}^1\Pi-\textrm{X}^1\Sigma^+$ band system of carbon monoxide, which has been detected in six highly redshifted galaxies ($z=1.6-2.7$), is identified as a novel probe method to search for possible variations of the proton-electron mass ratio ($\mu$) on cosmological time scales. Laboratory wavelengths of the spectral lines of the A-X ($v$,0) bands for $v=0-9$ have been determined at an accuracy of $\Delta\lambda/\lambda=1.5 \times 10^{-7}$ through VUV Fourier-transform absorption spectroscopy, providing a comprehensive and accurate zero-redshift data set. For the (0,0) and (1,0) bands, two-photon Doppler-free laser spectroscopy has been applied at the $3 \times 10^{-8}$ accuracy level, verifying the absorption data. Sensitivity coefficients $K_{\mu}$ for a varying $\mu$ have been calculated for the CO A-X bands, so that an operational method results to search for $\mu$-variation.Comment: 7 pages (main article), 3 figures, includes supplementary materia

High-resolution Fourier-transform XUV photoabsorption spectroscopy of 14N15N

The first comprehensive high-resolution photoabsorption spectrum of 14N15N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet (XUV) and span 100,000-109,000 cm-1 (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N2 that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schroedinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.Comment: 14 pages, 8 figures, one data archiv

Effect of electronic angular momentum exchange on photoelectron anisotropy following the two-colour ionization of krypton atoms

We present photoelectron energy and angular distributions for resonant two-photon ionization via several low-lying Rydberg states of atomic Kr. The experiments were performed by using synchrotron radiation to pump the Rydberg states and a continuous wave laser to probe them. Photoelectron images, recorded with both linear and circular polarized pump and probe light, were obtained in coincidence with mass-analyzed Kr ions. The photoelectron angular distributions and branching ratios for direct ionization into the Kr+ 2P3/2 and 2P1/2 spin-orbit continua show considerable dependence on the intermediate level, as well as on the polarizations of the pump and probe light. Photoelectron angular distributions were also recorded with several polarization combinations following two-colour excitation of the (2P1/2)5f[5/2]2 autoionizing resonance. These results are compared with the results of recent work on the corresponding autoionizing resonance in atomic Xe

Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light

Electron–nuclei coupling accompanying excitation and relaxation processes is a fascinating phenomenon in molecular dynamics. A striking and unexpected example of such coupling is presented here in the context of photoelectron circular dichroism measurements on randomly oriented, chiral methyloxirane molecules, unaffected by any continuum resonance. Here, we report that the forward-backward asymmetry in the electron angular distribution, with respect to the photon axis, which is associated with photoelectron circular dichroism can surprisingly reverse direction according to the ion vibrational mode excited. This vibrational dependence represents a clear breakdown of the usual Franck–Condon assumption, ascribed to the enhanced sensitivity of photoelectron circular dichroism (compared with other observables like cross-sections or the conventional anisotropy parameter-β) to the scattering phase off the chiral molecular potential, inducing a dependence on the nuclear geometry sampled in the photoionization process. Important consequences for the interpretation of such dichroism measurements within analytical contexts are discussed

High-Resolution Oscillator Strength Measurements of the v\u27 = 0,1 Bands of the B-X, C-X, and E-X Systems in Five Isotopologues of Carbon Monoxide

We report oscillator strengths for six strong vibrational bands between 105.0 and 115.2 nm, associated with transitions from the v = 0 level of the X 1Σ+ ground state to the v = 0 and 1 levels of the B 1Σ+, C 1Σ+, and E 1Π states, in 12C16O, 12C17O, 12C18O, 13C16O, and 13C18O. These measurements extend the development of a comprehensive database of line positions, oscillator strengths, and linewidths of photodissociating transitions for all astrophysically relevant CO isotopologues. The E–X bands, in particular, play central roles in CO photodissociation and fractionationmodels of interstellar clouds and circumstellar disks including the early solar nebula. The resolving powers of the room-temperature measurements, R = 300,000–400,000, allow for the analysis of individual line strengths within bands; the measurements reveal J-dependences in the branch intensities of the C(v = 0,1)–X(0) and E(v = 0,1)–X(0) bands in all isotopologues. Minimal or no isotopologue dependence was found in the f-values of the C(v = 0,1)–X(0) and E(v = 0,1)–X(0) bands at a ∼5% uncertainty level. Revised dissociation branching ratios for the C(v = 0,1) and E(v = 0,1) levels are computed based on these f-values. The weak isotopologue dependence of the f-values presented here eliminates this mechanism as an explanation for the large 17O enrichments seen in recent laboratory photolysis experiments on CO at wavelengths from 105 to 108 nm

LDL aggregation susceptibility is higher in healthy South Asian compared with white Caucasian men

BACKGROUND: South Asians are more prone to develop atherosclerotic cardiovascular disease (ASCVD) compared with white Caucasians, which is not fully explained by classical risk factors. We recently reported that the presence of aggregation-prone low-density lipoprotein (LDL) in the circulation is associated with increased ASCVD mortality. OBJECTIVE: We hypothesized that LDL of South Asians is more prone to aggregate, which may be explained by differences in their LDL lipid composition. METHODS: In this cross-sectional hypothesis-generating study, LDL was isolated from plasma of healthy South Asians (n = 12) and age- and BMI-matched white Caucasians (n = 12), and its aggregation susceptibility and lipid composition were analyzed. RESULTS: LDL from South Asians was markedly more prone to aggregate compared with white Caucasians. Among all measured lipids, sphingomyelin 24:0 and triacylglycerol 56:8 showed the highest positive correlation with LDL aggregation. In addition, LDL from South Asians was enriched in arachidonic acid containing phosphatidylcholine 38:4 and had less phosphatidylcholines and cholesteryl esters containing monounsaturated fatty acids. Interestingly, body fat percentage, which was higher in South Asians (+26%), positively correlated with LDL aggregation and highly positively correlated with triacylglycerol 56:8, sphingomyelin 24:0, and total sphingomyelin. CONCLUSIONS: LDL aggregation susceptibility is higher in healthy young South Asians compared with white Caucasians. This may be partly explained by the higher body fat percentage of South Asians, leading to sphingomyelin enrichment of LDL. We anticipate that the presence of sphingomyelin-rich, aggregation -prone LDL particles in young South Asians may increase LDL accumulation in the arterial wall and thereby contribute to their increased risk of developing ASCVD later in life. (C) 2019 National Lipid Association. Published by Elsevier Inc.Peer reviewe