Decay pathways for protonated and deprotonated adenine molecules.

We have measured fragment mass spectra and total destruction cross sections for protonated and deprotonated adenine following collisions with He at center-of-mass energies in the 20-240 eV range. Classical and ab initio molecular dynamics simulations are used to provide detailed information on the fragmentation pathways and suggest a range of alternative routes compared to those reported in earlier studies. These new pathways involve, for instance, losses of HNC molecules from protonated adenine and losses of NH2 or C3H2N2 from deprotonated adenine. The present results may be important to advance the understanding of how biomolecules may be formed and processed in various astrophysical environments.

Mutual Neutralization of O

We have measured total absolute cross sections for the mutual neutralization (MN) of O^{-} with O^{+} and N^{+}. A fine resolution (of about 50 meV) in the kinetic energy spectra of the product neutral atoms allows unique identification of the atomic states participating in the mutual neutralization process. Cross sections and branching ratios have also been calculated down to 1 meV center-of-mass collision energy for these two systems, with a multichannel Landau-Zener model and an asymptotic method for the ionic-covalent coupling matrix elements. The importance of two-electron processes in one-electron transfer is demonstrated by the dominant contribution of a core-excited configuration of the nitrogen atom in N^{+}+O^{-} collisions. This effect is partially accounted for by introducing configuration mixing in the evaluation of coupling matrix elements.

Erratum: Rotationally Cold OH

This corrects the article DOI: 10.1103/PhysRevLett.119.073001.

Rotationally Cold OH

We apply near-threshold laser photodetachment to characterize the rotational quantum level distribution of OH^{-} ions stored in the cryogenic ion-beam storage ring DESIREE at Stockholm University. We find that the stored ions relax to a rotational temperature of 13.4±0.2 K with 94.9±0.3% of the ions in the rotational ground state. This is consistent with the storage ring temperature of 13.5±0.5 K as measured with eight silicon diodes but in contrast to all earlier studies in cryogenic traps and rings where the rotational temperatures were always much higher than those of the storage devices at their lowest temperatures. Furthermore, we actively modify the rotational distribution through selective photodetachment to produce an OH^{-} beam where 99.1±0.1% of approximately one million stored ions are in the J=0 rotational ground state. We measure the intrinsic lifetime of the J=1 rotational level to be 145±28 s.

New light shed on charge transfer in fundamental H+ + H2 collisions.

There is no consensus on the magnitude and shape of the charge transfer cross section in low-energy H+ + H2 collisions, in spite of the fundamental importance of these collisions. Experiments have thus been carried out in the energy range 15≤E≤5000 eV. The measurements invalidate previous recommended data for E≤200 eV and confirm the existence of a local maximum around 45 eV, which was predicted theoretically. Additionally, vibrationally resolved cross sections allow us to investigate the evolution of the underlying charge transfer mechanism as a function of E.

DESIREE electrospray ion source test bench and setup for collision induced dissociation experiments.

In this paper, we give a detailed description of an electrospray ion source test bench and a single-pass setup for ion fragmentation studies at the Double ElectroStatic Ion Ring ExpEriment infrastructure at Stockholm University. This arrangement allows for collision-induced dissociation experiments at the center-of-mass energies between 10 eV and 1 keV. Charged fragments are analyzed with respect to their kinetic energies (masses) by means of an electrostatic energy analyzer with a wide angular acceptance and adjustable energy resolution.

Dianion diagnostics in DESIREE: High-sensitivity detection of Cn2- from a sputter ion source.

A sputter ion source with a solid graphite target has been used to produce dianions with a focus on carbon cluster dianions, Cn2-, with n = 7-24. Singly and doubly charged anions from the source were accelerated together to kinetic energies of 10 keV per atomic unit of charge and injected into one of the cryogenic (13 K) ion-beam storage rings of the Double ElectroStatic Ion Ring Experiment facility at Stockholm University. Spontaneous decay of internally hot Cn2- dianions injected into the ring yielded Cn- anions with kinetic energies of 20 keV, which were counted with a microchannel plate detector. Mass spectra produced by scanning the magnetic field of a 90° analyzing magnet on the ion injection line reflect the production of internally hot C72- - C242- dianions with lifetimes in the range of tens of microseconds to milliseconds. In spite of the high sensitivity of this method, no conclusive evidence of C62- was found while there was a clear C72- signal with the expected isotopic distribution. This is consistent with earlier experimental studies and with theoretical predictions. An upper limit is deduced for a C62- signal that is two orders-of-magnitude smaller than that for C72-. In addition, CnO2- and CnCu2- dianions were detected.

Threshold energies for single-carbon knockout from polycyclic aromatic hydrocarbons.

We have measured absolute cross sections for ultrafast (femtosecond) single-carbon knockout from polycyclic aromatic hydrocarbon (PAH) cations as functions of He­PAH center-of-mass collision energy in the 10­200 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).

Generation of neutral atomic beams utilizing photodetachment by high power diode laser stacks.

We demonstrate the use of high power diode laser stacks to photodetach fast hydrogen and carbon anions and produce ground term neutral atomic beams. We achieve photodetachment efficiencies of ∼7.4% for H(-) at a beam energy of 10 keV and ∼3.7% for C(-) at 28 keV. The diode laser systems used here operate at 975 nm and 808 nm, respectively, and provide high continuous power levels of up to 2 kW, without the need of additional enhancements like optical cavities. The alignment of the beams is straightforward and operation at constant power levels is very stable, while maintenance is minimal. We present a dedicated photodetachment setup that is suitable to efficiently neutralize the majority of stable negative ions in the periodic table.

Laser-intensity dependent vibrational excitation and alignment of molecular ions in the ultrafast multiphoton regime.

H2 molecules were ionized in the ultrafast (approximately 150 fs) multiphoton regime (263 nm, approximately 10(13) W cm(-2)). Earlier experiments investigated the kinetic energies of electrons or ions only. Using a unique experiment, we show that the vibrational excitation of molecular ions contains essential information about the dynamics of the process. In addition, we prove some earlier interpretations wrong. A realistic model based on vibronically excited intermediates, Stark shifting into resonance, reproduces the measurements, demonstrating that resonances continue to be important in the femtosecond regime. This eventually enables ultrafast control of the vibrational excitation of molecular ions, which is relevant to the whole field of molecular physics and physical chemistry.

Intense-laser-field ionization of molecular hydrogen in the tunneling regime and its effect on the vibrational excitation of H2+.

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.