Kinetic energy release in electron-induced decay reactions of molecular ions: C3H8+ and C3H7+

We have measured the kinetic energy release (KER) distributions for electron-induced dissociation of mass-selected molecular parent and fragment ions of propane. They are compared with distributions determined for spontaneous (metastable) dissociation. The average KER for induced dissociation of C3H8+ into C3H7+ is 13.2 +/- 1.2 meV, about 42% larger than for the spontaneous reaction. This large difference is attributed to the dramatically reduced time at which the induced reaction can be sampled. In contrast, the KER for dissociation of C3H7+ into C3H5+, which is characterized by a large reverse activation energy, is hardly affected by the experimental time scale. (C) 2000 American Institute of Physics. [S0021-9606(00)00826-6]

High-resolution kinetic energy release distributions and dissociation energies for fullerene ions C(n)(+), 42 \u3c= n \u3c= 90

We have measured the kinetic energy released in the unimolecular dissociation of fullerene ions, C(n)(+)--\u3eC(n-2)(+)+C(2), for sizes 42less than or equal tonless than or equal to90. A three-sector-field mass spectrometer equipped with two electric sectors has been used in order to ensure that contributions from isotopomers of different masses do not distort the experimental kinetic energy release distributions. We apply the concept of microcanonical temperature to derive from these data the dissociation energies of fullerene cations. They are converted to dissociation energies of neutral fullerenes with help of published adiabatic ionization energies. The results are compared with literature values. (C) 2004 American Institute of Physics

High resolution measurements of kinetic energy release distributions of neon, argon, and krypton cluster ions using a three sector field mass spectrometer

Using a newly constructed three sector field mass spectrometer (resulting in a BE1E2 field configuration) we have measured the kinetic energy release distributions of neon, argon, and krypton cluster ions. In the present study we used the first two sectors, B and E1, constituting a high resolution mass spectrometer, to select the parent ions in terms of mass, charge, and energy, and studied the decay of those ions in the third field free region. Due to the improved mass resolution we were able to extend earlier studies carried out with a two sector field machine, where an upper size limit arose from the fact that several isotopomers contribute to a decaying parent ion beam when the cluster size exceeds a certain value. Furthermore we developed a new data analysis. It allows us to model also fragment ion peaks that are a superposition of different decay reactions and thus we can determine the average kinetic energy release for all decay reactions of a given cluster ion. In a further step we used these results to determine the binding energies of cluster ions Rg(n) (ngreater than or equal to10) by applying finite heat bath theory. The smaller sizes have not been included in this analysis, because the validity of finite heat bath theory becomes questionable below napproximate to10. The present average kinetic energy releases and binding energies are compared with other experiments and various calculations. (C) 2004 American Institute of Physics

Mechanisms and dynamics of the metastable decay in Ar-2(+)

A detailed experimental as well as theoretical investigation of the properties of the metastable dissociation Ar-2(+)--\u3eAr++Ar is presented. The mass-analyzed ion kinetic energy (MIKE) scan technique has been performed using a three sector field mass spectrometer. The possible mechanisms of the metastability of Ar-2(+) have been examined and the observed decay process is assigned to the II(1/2)(u)--\u3eI(1/2)(g) bound to continuum radiative transition, in agreement with earlier work. The calculation of the theoretical shape of the kinetic energy release distribution of fragment ions allowed us to construct the theoretical MIKE peak and compare it with the raw experimental data. The accuracy of various sets of potential energy curves for Ar-2(+) is discussed, as well as the way of production of the metastable Ar-2(+)[II(1/2)(u)] electronic state by electron impact. Excellent agreement between the experimental data and theoretical model has been observed. (C) 2004 American Institute of Physics

Kinetic-energy release in Coulomb explosion of metastable C3H52+

C3H52+, formed by electron impact ionization of propane, undergoes metastable decay into C2H2++CH3+. We have monitored this reaction in a magnetic mass spectrometer of reversed geometry that is equipped with two electric sectors (BEE geometry). Three different techniques were applied to identify the fragment ions and determine the kinetic-energy release (KER) of spontaneous Coulomb explosion of C3H52+ in the second and third field free regions of the mass spectrometer. The KER distribution is very narrow, with a width of about 3% [root-mean square standard deviation]. An average KER of 4.58+/-0.15 eV is derived from the distribution. High level ab initio quantum-chemical calculations of the structure and energetics of C3H52+ are reported. The activation barrier of the reverse reaction, CH3++C2H2+ (vinylidene), is computed. The value closely agrees with the experimental average KER, thus indicating that essentially all energy available in the reaction is partitioned into kinetic energy. (C) 2003 American Institute of Physics

Formation of even-numbered hydrogen cluster cations in ultracold helium droplets

Neutral hydrogen clusters are grown in ultracold helium nanodroplets by successive pickup of hydrogen molecules. Even-numbered hydrogen cluster cations are observed upon electron-impact ionization with and without attached helium atoms and in addition to the familiar odd-numbered H(n)(+). The helium matrix affects the fragmentation dynamics that usually lead to the formation of overwhelmingly odd-numbered H(n)(+). The use of high-resolution mass spectrometry allows the unambiguous identification of even-numbered H(n)(+) up to n congruent to 120 by their mass excess that distinguishes them from He(n)(+), mixed He(m)H(n)(+), and background ions. The large range in size of these hydrogen cluster ions is unprecedented, as is the accuracy of their definition. Apart from the previously observed magic number n = 6, pronounced drops in the abundance of even-numbered cluster ions are seen at n = 30 and 114, which suggest icosahedral shell closures at H(6)(+)(H(2))(12) and H(6)(+)(H(2))(54). Possible isomers of H(6)(+) are identified at the quadratic configuration interaction with inclusion of single and double excitations (QCISD)/aug-cc-pVTZ level of theory (C) 2008 American Institute of Physics. [DOI: 10.1063/1.3035833

Doubly Charged Coronene Clusters – Much Smaller than Previously Observed

The smallest doubly charged coronene cluster ions reported so far, Cor152+, were produced by charge exchange between bare coronene clusters and He2+ [H. A. B. Johansson et al., Phys. Rev. A 84, 043201 (2011)]. These dications are at least five times larger than the estimated Rayleigh limit, i.e., the size at which the activation barrier for charge separation vanishes. Such a large discrepancy is unheard of for doubly charged atomic or molecular clusters. Here we report the mass spectrometric observation of doubly charged coronene trimers, produced by electron ionization of helium nanodroplets doped with coronene. The observation implies that Cor32+ features a non-zero fission barrier too large to overcome under the present experimental conditions. The height of the barriers for the dimer and trimer has been estimated by means of density functional theory calculations. A sizeable barrier for the trimer has been revealed in agreement with the experimental findings

Lifetimes of C-60(2-) and C-70(2-) dianions in a storage ring

C-60(2-) and C-70(2-) dianions have been produced by electrospray of the monoanions and subsequent electron pickup in a Na vapor cell. The dianions were stored in an electrostatic ring and their decay by electron emission was measured up to 1 s after injection. While C-70(2-) ions are stable on this time scale, except for a small fraction of the ions which have been excited by gas collisions, most of the C-60(2-) ions decay on a millisecond time scale, with a lifetime depending strongly on their internal temperature. The results can be modeled as decay by electron tunneling through a Coulomb barrier, mainly from thermally populated triplet states about 120 meV above a singlet ground state. At times longer than about 100 ms, the absorption of blackbody radiation plays an important role for the decay of initially cold ions. The tunneling rates obtained from the modeling, combined with WKB estimates of the barrier penetration, give a ground-state energy 200 +/- 30 meV above the energy of the monoanion plus a free electron and a ground-state lifetime of the order of 20 s. (c) 2006 American Institute of Physics

Adsorption of Helium and Hydrogen on Triphenylene and 1,3,5-Triphenylbenzene

The adsorption of helium or hydrogen on cationic triphenylene (TPL, C18H12), a planar polycyclic aromatic hydrocarbon (PAH) molecule, and of helium on cationic 1,3,5-triphenylbenzene (TPB, C24H18), a propeller-shaped PAH, is studied by a combination of high-resolution mass spectrometry and classical and quantum computational methods. Mass spectra indicate that HenTPL+ complexes are particularly stable if n = 2 or 6, in good agreement with the quantum calculations which show that for these sizes the helium atoms are strongly localized on either side of the central carbon ring for n = 2 and on either side of the three outer rings for n = 6. Theory suggests that He14TPL+ is also particularly stable, with the helium atoms strongly localized on either side of the central and outer rings plus the vacancies between the outer rings. For HenTPB+ the mass spectra hint at enhanced stability for n = 2, 4 and, possibly, 11. Here the agreement with theory is less satisfactory, probably because TPB+ is a highly fluxional molecule. In the global energy minimum, the phenyl groups are rotated in the same direction but when the zero-point harmonic correction is included, a structure with one phenyl group being rotated opposite to the other two becomes lower in energy. The energy barrier between the two isomers is very small, and TPB+ could be in a mixture of symmetric and antisymmetric states, or possibly even vibrationally delocalized

Phenanthrene: Establishing Lower and Upper Bounds to the Binding Energy of a Very Weakly Bound Anion

Quite a few molecules do not form stable anions that survive the time needed for their detection; their electron affinities (EA) are either very small or negative. How does one measure the EA if the anion cannot be observed? Or, at least, can one establish lower and upper bounds to their EA? We propose two approaches that provide lower and upper bounds. We choose the phenanthrene (Ph) molecule whose EA is controversial. Through competition between helium evaporation and electron detachment in HenPh- clusters, formed in helium nanodroplets, we estimate the lower bound of the vertical detachment energy (VDE) of Ph- as about – 3 meV. In the second step, Ph is complexed with calcium whose electron affinity is just 24.55 meV. When CaPh- ions are collided with a thermal gas of argon, one observes Ca- product ions but no Ph-, suggesting that the EA of Ph is below that of Ca