The B2Π−^2\Pi-X2Π^2\Pi electronic origin band of 13^{13}C6_6H

The rotationally resolved spectrum of the B$^2\Pi-$X$^2\Pi$ electronic origin band transition of $^{13}$C$_6$H is presented. The spectrum is recorded using cavity ring-down spectroscopy in combination with supersonic plasma jets by discharging a $^{13}$C$_2$H$_2$/He/Ar gas mixture. A detailed analysis of more than a hundred fully-resolved transitions allows for an accurate determination of the spectroscopic parameters for both the ground and electronically excited state of $^{13}$C$_6$H.Comment: 4 pages, 1 figure, 2 table

C60+_{60}^+ and the Diffuse Interstellar Bands: An Independent Laboratory Check

In 2015, Campbell et al. (Nature 523, 322) presented spectroscopic laboratory gas phase data for the fullerene cation, C$_{60}^+$, that coincide with reported astronomical spectra of two diffuse interstellar band (DIB) features at 9633 and 9578 \AA. In the following year additional laboratory spectra were linked to three other and weaker DIBs at 9428, 9366, and 9349 \AA. The laboratory data were obtained using wavelength-dependent photodissociation spectroscopy of small (up to three) He-tagged C$_{60}^+-$He$_n$ ion complexes, yielding rest wavelengths for the bare C$_{60}^+$ cation by correcting for the He-induced wavelength shifts. Here we present an alternative approach to derive the rest wavelengths of the four most prominent C$_{60}^+$ absorption features, using high resolution laser dissociation spectroscopy of C$_{60}^+$ embedded in ultracold He droplets. Accurate wavelengths of the bare fullerene cation are derived based on linear wavelength shifts recorded for He$_n$C$_{60}^+$ species with $n$ up to 32. A careful analysis of all available data results in precise rest wavelengths (in air) for the four most prominent C$_{60}^+$ bands: 9631.9(1) \AA, 9576.7(1) \AA, 9427.5(1) \AA, and 9364.9(1) \AA. The corresponding band widths have been derived and the relative band intensity ratios are discussed

A Spectroscopic Survey of Electronic Transitions of C6_6H, 13^{13}C6_6H, and C6_6D

Electronic spectra of C$_6$H are measured in the $18\,950-21\,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manifold of the B$^2\Pi$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $\nu_6$ mode associated with the C-C bond vibration and the $\nu_4$ and $\nu_3$ modes associated with C$\equiv$C triple bonds. For the two lowest $\nu_{11}$ and $\nu_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $\mu^2\Sigma$($\nu_{11}$) and both $\mu^2\Sigma$($\nu_{10}$) and $\kappa^2\Sigma$($\nu_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $\mu^2\Sigma$($\nu_9$) and $\mu^2\Sigma$($\nu_8$) levels. In the excitation region below the first non-degenerate vibration ($\nu_6$), some $^2\Pi-^{2}\Pi$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2\Pi-^{2}\Pi$ transition found above the $\nu_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2\Pi$ state of C$_6$H is derived and presented.Comment: Accepted for publication in The Journal of Physical Chemistry A (26 July 2016

Spectroscopic Survey of Electronic Transitions of C₆H, ¹³C₆H, and C₆D

Electronic spectra of C₆H are measured in the 18 950–21 100 cm^–1 domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)­bands of C₆H are presented, all probing the vibrational manifold of the B²Π electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for ¹³C₆H and C₆D), predictions from <i>ab initio</i> calculations, and rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the 0₀⁰ origin band, three nondegenerate stretching vibrations along the linear backbone of the C₆H molecule are assigned: the ν₆ mode associated with the C–C bond vibration and the ν₄ and ν₃ modes associated with CC triple bonds. For the two lowest ν₁₁ and ν₁₀ bending modes, a Renner–Teller analysis is performed identifying the μ²Σ­(ν₁₁) and both μ²Σ­(ν₁₀) and κ²Σ­(ν₁₀) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as μ²Σ­(ν₉) and μ²Σ­(ν₈) levels. In the excitation region below the first nondegenerate vibration (ν₆), some ²Π–²Π transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a ²Π ²Π transition found above the ν₆ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B²Π state of C₆H is derived and presented

The EDIBLES survey

We report cosmic ray ionization rates toward ten reddened stars studied within the framework of the EDIBLES (ESO Diffuse Interstellar Bands Large Exploration Survey) program, using the VLT-UVES. For each sightline, between two and ten individual rotational lines of OH+ have been detected in its (0,0) and (1,0) A3Π − X3Σ− electronic band system. This allows constraining of OH+ column densities toward different objects. Results are also presented for 28 additional sightlines for which only one or rather weak signals are found. An analysis of these data makes it possible to derive the primary cosmic ray ionization rate ζp in the targeted diffuse interstellar clouds. For the ten selected targets, we obtain a range of values for ζp equal to (3.9–16.4) × 10−16 s−1. These values are higher than the numbers derived in previous detections of interstellar OH+ in the far-infrared/submillimeter-wave regions and in other near-ultraviolet studies. This difference is a result of using new OH+ oscillator strength values and a more complete picture of all relevant OH+ formation and destruction routes (including the effect of proton recombinations on PAHs), and the relatively high N(OH+) seen toward those ten targets