H2 molecules were ionized by Ti:sapphire (45 fs, 800 nm) and Nd-doped yttrium aluminum garnet lasers (6 ns, 1064 nm). The relative populations of the vibrational levels of the H+2 ions were determined and found to be concentrated in the lowest vibrational levels. Tunneling ionization calculations with exact field-modified potential curves reproduce the experimental results. The reason for the departure from conventional Franck-Condon-like distributions is the rapid variation of the ionization rate with internuclear distance.

A recent study of soft X-ray absorption in native and hydrogenated coronene cations, C 24 H + 12+m m = 0-7, led to the conclusion that additional hydrogen atoms protect (interstellar) Polycyclic Aromatic Hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014)]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C 16 H + 10+m , m = 0, 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.

We have investigated the chemistry of C + H + 3 forming CH + , CH + 2 , and CH + 3 . These reactions are believed to be some of the key gas-phase astrochemical processes initiating the formation of organic molecules in molecular clouds. For this work we have constructed a novel merged fast-beams apparatus which overlaps a beam of molecular ions onto a beam of ground-term neutral atoms. Here we describe the apparatus in detail and present cross section data for forming CH + and CH + 2 at relative energies from ≈ 9 meV to ≈ 20 and 3 eV, respectively. Measurements were performed for statistically populated C( 3 P J ) in the ground term reacting with hot H + 3 (at an internal temperature of ∼ 2, 550 K). Using these data we have derived rate coefficients for translational temperatures from ≈ 72 K to ≈ 2.3 ×10 5 and 3.4 ×10 4 K, respectively. For the formation of CH + 3 we are able only to put an upper limit on the rate coefficient. Our results for CH +

We have measured absolute cross sections for ultrafast (femtosecond) single-carbon knockout from polycyclic aromatic hydrocarbon (PAH) cations as functions of He–PAH center-of-mass collision energy in the 10–200 eV range. Classical molecular dynamics (MD) simulations cover this range and extend up to 105 eV. The shapes of the knockout cross sections are well-described by a simple analytical expression yielding experimental and MD threshold energies of EthExp = 32.5 ± 0.4 eV and EthMD = 41.0 ± 0.3 eV, respectively. These are the first measurements of knockout threshold energies for molecules isolated in vacuo. We further deduce semiempirical (SE) and MD displacement energies, i.e., the energy transfers to the PAH molecules at the threshold energies for knockout, of TdispSE = 23.3 ± 0.3 eV and TdispMD = 27.0 ± 0.3 eV. The semiempirical results compare favorably with measured displacement energies for graphene (Tdisp = 23.6 eV).

Ultraslow radiative cooling lifetimes and adiabatic detachment energies for three astrochemically relevant anions, C − n (n = 3 − 5), are measured using the Double ElectroStatic Ion Ring ExpEriment (DESIREE) infrastructure at Stockholm University. DESIREE maintains a background pressure of ≈10 −14 mbar and temperature of ≈13 K, allowing storage of mass-selected ions for hours and providing conditions coined a "molecular cloud in a box". Here, we construct two-dimensional (2D) photodetachment spectra for the target anions by recording photodetachment signal as a function of irradiation wavelength and ion storage time (seconds to minute timescale). Ion cooling lifetimes, which are associated with infrared radiative emission, are extracted from the 2D photodetachment spectrum for each ion by tracking the disappearance of vibrational hot-band signal with ion storage time, giving 1 e cooling lifetimes of 3.1±0.1 s (C − 3 ), 6.8±0.5 s (C − 4 ) and 24±5 s (C − 5 ). Fits of the photodetachment spectra for cold ions, i.e. those stored for at least 30 s, provides adiabatic detachment energies in good agreement with values from laser photoelectron spectroscopy. Ion cooling lifetimes are simulated using a Simple Harmonic Cascade model, finding good agreement with experiment and providing a mode-by-mode understanding of the radiative cooling properties. The 2D photodetachment strategy and radiative cooling modeling developed in this study could be applied to investigate the ultraslow cooling dynamics of wide range of molecular anions. arXiv:1909.07087v1 [physics.atm-clus]