On the impact of multi-reference character of small transition metal compounds on their bond dissociation energies.

Determining the multi-reference character of a molecular system and its impact on the limits within which its properties may be calculated accurately by different quantum chemical methods remains a difficult yet important task in computational chemistry. Especially, transition metal compounds continue to frequently provide a challenge to quantum chemists in this regard. In this work, we construct, analyze, and evaluate different computational protocols to determine the impact of the multi-reference character of transition metal compounds on their bond dissociation energies using a set of reference data for 60 diatomic molecules. We find that the fractional orbital density approach allows to determine two global indicators on a physically sound basis. These can subsequently be used to classify the assessed set of molecules with high accuracy into categories of systems for which their multi-reference character matters substantially for their bond dissociation energies and for which it does not. A comparison with earlier suggested thresholds for classification of molecular systems due to their multi-reference character suggests that our approaches yield substantially better performance.

Total and partial electron impact ionization cross sections of fusion-relevant diatomic molecules.

We report calculations of total (and absolute) electron-impact ionization cross sections (EICSs) for the fusion-relevant diatomic molecular species BeH, BeN, BeO, WH, WBe, WN, WO, O2, and N2 by means of the Deutsch-Märk and the binary-encounter-Bethe methods in the energy range from threshold to 10 keV. In addition, we discuss an empirical scheme to estimate partial cross sections from the total ones based on reaction energetics and empirical threshold laws and explore its accuracy by assessing available experimental data on total and partial EICSs. Finally, we also report parameters obtained by fitting the calculated cross sections to an expression commonly used in fusion edge plasma modeling.

Hydroperoxyl radical and formic acid formation from common DNA stabilizers upon low energy electron attachment.

2-Amino-2-(hydroxymethyl)-1,3-propanediol (TRIS) and ethylenediaminetetraacetic acid (EDTA) are key components of biological buffers and are frequently used as DNA stabilizers in irradiation studies. Such surface or liquid phase studies are done with the aim to understand the fundamental mechanisms of DNA radiation damage and to improve cancer radiotherapy. When ionizing radiation is used, abundant secondary electrons are formed during the irradiation process, which are able to attach to the molecular compounds present on the surface. In the present study we experimentally investigate low energy electron attachment to TRIS and methyliminodiacetic acid (MIDA), an analogue of EDTA, supported by quantum chemical calculations. The most prominent dissociation channel for TRIS is through hydroperoxyl radical formation, whereas the dissociation of MIDA results in the formation of formic and acetic acid. These compounds are well-known to cause DNA modifications, like strand breaks. The present results indicate that buffer compounds may not have an exclusive protecting effect on DNA as suggested previously.

Temperature dependence of dissociative electron attachment to bromo-chlorotoluene isomers: Competition between detachment of Cl- and Br.

Dissociative electron attachment to three isomers of bromo-chlorotoluene was investigated in the electron energy range from 0 to 2 eV for gas temperatures in the range of 392-520 K using a crossed electron-molecular beam apparatus with a temperature regulated effusive molecular beam source. For all three molecules, both Cl- and Br- are formed. The ion yields of both halogenides show a pronounced temperature effect. In the case of Cl- and Br-, the influence of the gas temperature can be observed at the threshold peak close to 0 eV. The population of molecules that have some of their out-of-plane modes excited varies strongly in the temperature range investigated, indicating that such vibrations might play a role in the energy transfer towards bond breaking. Potential energy curves for the abstraction of Cl- and Br- were calculated and extrapolated into the metastable domain. The barriers in the diabatic curves approximated in this way agree well with the ones derived from the temperature dependence observed in the experiments.

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.

Isomer Selectivity in Low-Energy Electron Attachment to Nitroimidazoles.

Low-energy electrons effectively decompose the isomers 2-nitroimidazole and 4(5)-nitroimidazole by dissociative electron attachment (DEA) into a variety of fragment anions and radicals. The present study shows that a distinct selectivity for the two isomers occurs in the DEA reactions. Several new decay channels are observed for 2-nitroimidazole, including a dominant one leading to the loss of molecular H2 O by attachment of a low-energy electron. In contrast, the loss of a single hydrogen atom is a much more efficient reaction in DEA to 4(5)-nitroimidazole. Quantum chemical calculations were carried out to explain the pronounced isomer effect found in the DEA experiment. Although the free energies of the reactions are similar for the different isomers, the very different natures of the dipole-bound states and valence-bound anions lead to preference for or hindrance of a particular dissociation channel. Nitroimidazolic compounds are considered as radiosensitizing compounds in tumor radiation therapy. The enhanced formation of fragments, including the highly reactive hydroxyl radical, in DEA to 2-nitroimidazole suggests that it may be a more efficient radiosensitizing agent than 4(5)-nitroimidazoles.

Formation of Negative Ions upon Dissociative Electron Attachment to the Astrochemically Relevant Molecule Aminoacetonitrile.

Aminoacetonitrile (NH2CH2CN, AAN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. It is a very important molecule in the Strecker diagram explaining the formation of amino acids. In the present investigation, dissociative electron attachment to NH2CN was studied in a crossed electron-molecular beams experiment in the electron energy range from about 0 to 17 eV. In this electron energy range, the following six anionic species were detected: C2H3N2(-), C2H2N2(-), C2H2N(-), C2HN(-), CN(-), and NH2(-). Possible reaction channels for all the measured negative ions are discussed, and the experimental results are compared with calculated thermochemical thresholds of the observed anions. Similar to other nitrile and aminonitrile compounds, the main anions detected were the negatively charged nitrile group, the dehydrogenated parent molecule, and the amino group. No parent anion was observed. Low anion yields were observed indicating that AAN is less prone to electron capture. Therefore, AAN can be considered to exhibit a relatively long lifetime under typical conditions in outer space.

Low energy electron attachment to cyanamide (NH2CN).

Cyanamide (NH2CN) is a molecule relevant for interstellar chemistry and the chemical evolution of life. In the present investigation, dissociative electron attachment to NH2CN has been studied in a crossed electron-molecular beams experiment in the electron energy range from about 0 eV to 14 eV. The following anionic species were detected: NHCN(-), NCN(-), CN(-), NH2(-), NH(-), and CH2(-). The anion formation proceeds within two broad electron energy regions, one between about 0.5 and 4.5 eV and a second between 4.5 and 12 eV. A discussion of possible reaction channels for all measured negative ions is provided. The experimental results are compared with calculations of the thermochemical thresholds of the anions observed. For the dehydrogenated parent anion, we explain the deviation between the experimental appearance energy of the anion with the calculated corresponding reaction threshold by electron attachment to the isomeric form of NH2CN--carbodiimide.

The interaction of He(-) with fullerenes.

The effects of interactions between He(-) and clusters of fullerenes in helium nanodroplets are described. Electron transfer from He(-) to (C60)n and (C70)n clusters results in the formation of the corresponding fullerene cluster dianions. This unusual double electron transfer appears to be concerted and is most likely guided by electron correlation between the two very weakly bound outer electrons in He(-). We suggest a mechanism which involves long range electron transfer followed by the conversion of He(+)into He2 (+), where formation of the He-He bond in He2 (+) releases sufficient kinetic energy for the cation and the dianion to escape their Coulombic attraction. By analogy with the corresponding dications, the observation of a threshold size of n ≥ 5 for formation of both (C60)n (2-) and (C70)n (2-) is attributed to Coulomb explosion rather than an energetic constraint. We also find that smaller dianions can be observed if water is added as a co-dopant. Other aspects of He(-) chemistry that are explored include its role in the formation of multiply charged fullerene cluster cations and the sensitivity of cluster dianion formation on the incident electron energy.

On the formation of (anionic) excited helium dimers in helium droplets.

Metastable atomic and molecular helium anions exhibiting high-spin quartet configurations can be produced in helium droplets via electron impact. Their lifetimes allow detection in mass spectrometric experiments. Formation of atomic helium anions comprises collision-induced excitation of ground state helium and concomitant electron capture. Yet the formation of molecular helium anions in helium droplets has been an unresolved issue. In this work, we explore the interaction of excited helium atoms exhibiting high-spin triplet configurations with ground state helium using the equation-of-motion coupled-cluster method. Transition barriers in the energetically lowest He*-He and He*(-)-He interaction potentials prevent molecule formation at the extremely low temperatures present in helium droplets. In contrast, some excited states allow a barrier-free formation of molecular helium (anions). Moreover, we show that the necessary excitation energies pinpoint (higher) resonances in recently recorded mass spectra and emend the assignment of those resonances that have previously been assigned to electron-impact ionization of ground state helium necessitating subsequent double-electron capture. Embedding molecules or molecular clusters in helium droplets is a predestined experimental technique for the study of phenomena at very low temperatures. Profound knowledge about active processes in the helium environment is required for a proper assessment of experimental data.

Upper limits to the reaction rate coefficients of C(n)(-) and C(n)H(-) (n = 2, 4, 6) with molecular hydrogen.

In the interstellar medium (ISM) ion­molecule reactions play a key role in forming complex molecules. Since 2006, after the radioastronomical discovery of the first of by now six interstellar anions, interest has grown in understanding the formation and destruction pathways of negative ions in the ISM. Experiments have focused on reactions and photodetachment of the identified negatively charged ions. Hints were found that the reactions of CnH(­) with H2 may proceed with a low (<10(­13) cm(3) s(­1)), but finite rate [Eichelberger, B.; et al. Astrophys. J. 2007, 667, 1283]. Because of the high abundance of molecular hydrogen in the ISM, a precise knowledge of the reaction rate is needed for a better understanding of the low-temperature chemistry in the ISM. A suitable tool to analyze rare reactions is the 22-pole radiofrequency ion trap. Here, we report on reaction rates for Cn(­) and CnH(­) (n = 2, 4, 6) with buffer gas temperatures of H2 at 12 and 300 K. Our experiments show the absence of these reactions with an upper limit to the rate coefficients between 4 × 10(­16) and 5 × 10(­15) cm(3) s(­1), except for the case of C2(­), which does react with a finite rate with H2 at low temperatures. For the cases of C2H(­) and C4H(­), the experimental results were confirmed with quantum chemical calculations. In addition, the possible influence of a residual reactivity on the abundance of C4H(­) and C6H(­) in the ISM were estimated on the basis of a gas-phase chemical model based on the KIDA database. We found that the simulated ion abundances are already unaffected if reaction rate coefficients with H2 were below 10(­14) cm(3) s(­1).

Modeling the intrusion of molecules into graphite: Origin and shape of the barriers.

We performed density functional theory calculations to explore the energetic and geometric aspects of the permeation of H2, BeH x , OH x (x = 1, 2) and CH y (y = 1-4) through the central hexagon of coronene. Coronene serves as a cluster model for extended graphene which can be regarded as the first layer of a graphite (0 0 0 1) surface. We compare the energy barriers encountered by these molecular projectiles with the ones that are obtained for atomic H, Be, C and O. The barriers are substantially lower if projectiles possess free valences that can bind to the carbon entity. Furthermore, for some of the species fragmentation is observed. Implications with respect to plasma-surface interaction are discussed.

Ethylene glycol revisited: Molecular dynamics simulations and visualization of the liquid and its hydrogen-bond network.

Molecular dynamics simulations of liquid ethylene glycol described by the OPLS-AA force field were performed to gain insight into its hydrogen-bond structure. We use the population correlation function as a statistical measure for the hydrogen-bond lifetime. In an attempt to understand the complicated hydrogen-bonding, we developed new molecular visualization tools within the Vish Visualization shell and used it to visualize the life of each individual hydrogen-bond. With this tool hydrogen-bond formation and breaking as well as clustering and chain formation in hydrogen-bonded liquids can be observed directly. Liquid ethylene glycol at room temperature does not show significant clustering or chain building. The hydrogen-bonds break often due to the rotational and vibrational motions of the molecules leading to an H-bond half-life time of approximately 1.5 ps. However, most of the H-bonds are reformed again so that after 50 ps only 40% of these H-bonds are irreversibly broken due to diffusional motion. This hydrogen-bond half-life time due to diffusional motion is 80.3 ps. The work was preceded by a careful check of various OPLS-based force fields used in the literature. It was found that they lead to quite different angular and H-bond distributions.

Formation of dianions in helium nanodroplets.

The formation of dianions in helium nanodroplets is reported for the first time. The fullerene cluster dianions (C60)n(2-) and (C70)n(2-) were observed by mass spectrometry for n≥5 when helium droplets containing the appropriate fullerene were subjected to electron impact at approximately 22 eV. A new mechanism for dianion formation is described, which involves a two-electron transfer from the metastable He(-) ion. As well as the prospect of studying other dianions at low temperature using helium nanodroplets, this work opens up the possibility of a wider investigation of the chemistry of He(-), a new electron-donating reagent.

Electron attachment to the dipeptide dialanine: influence of methylation on site selective dissociation reactions.

Gas phase dissociative electron attachment (DEA) measurements with methyl-dialanine, C(7)H(14)N(2)O(3), are performed in a crossed electron-molecular beam experiment at high energy resolution (∼120 meV). Anion efficiency yields as a function of the incident electron energy are obtained for the most abundant fragments up to electron energies of ∼15 eV. There is no evidence of molecular anion formation whereas the dehydrogenated closed shell anion (M-H)(-) is one of the most dominant reaction products. Quantum chemical calculations are performed to investigate the electron attachment process and to elucidate site selective bond cleavage in the (M-H)(-) DEA-channel. Previous DEA studies on dialanine have shown that (M-H)(-) formation proceeds through abstraction of a hydrogen atom from the carboxyl and amide groups, contributing to two distinct resonances at 0.81 and 1.17 eV, respectively [D. Gschliesser, V. Vizcaino, M. Probst, P. Scheier and S. Denifl, Chem.-Eur. J., 2012, 18, 4613-4619]. Here we show that by methylation of the carboxyl group, all (calculated) thresholds for H-loss from the different sites in the dialanine molecule are shifted up to a maximum of 1.4 eV. The lowest lying resonance observed experimentally for (M-H)(-) remains operative from the amide group at the electron energy of 2.4 eV due to the methylation. We further study methylation-induced effects on the unimolecular dissociation leading to a variety of negatively charged DEA products.

Numerical investigation of the elastic scattering of hydrogen (isotopes) and helium at graphite (0001) surfaces at beam energies of 1 to 4 eV using a split-step Fourier method.

We report simulations of the elastic scattering of atomic hydrogen isotopes and helium beams from graphite (0001) surfaces in an energy range of 1-4 eV. To this aim, we numerically solve a time-dependent Schrödinger equation using a split-step Fourier method. The hydrogen- and helium-graphite potentials are derived from density functional theory calculations using a cluster model for the graphite surface. We observe that the elastic interaction of tritium and helium with graphite differs fundamentally. Whereas the wave packets in the helium beam are directed to the centers of the aromatic cycles constituting the hexagonal graphite lattice, they are directed toward the rings in case of the hydrogen beams. These observations emphasize the importance of swift chemical sputtering for the chemical erosion of graphite and provide a fundamental justification of the graphite peeling mechanism observed in molecular dynamics studies. Our investigations imply that wave packet studies, complementary to classical atomistic molecular dynamics simulations open another angle to the microscopic view on the physics underlying the sputtering of graphite exposed to hot plasma.

Task-synchronized eye blink modulation neither requires visual stimulation nor active motor response and is modulated by task predictability.

It has been repeatedly shown that temporal task features are reflected in eye blink dynamics during attention tasks. Eye blinks occur with increased likeliness particularly when demands on external attention allocation are low. Both predictive, top-down and reactive, bottom-up processes were shown to be involved in blink regulation. However, whether temporal stimulus prediction is a generally active component of the attention system or rather specific to the visual domain has not been fully elaborated yet. By monitoring eye blinking of 99 students during an auditory attention task and analyzing particularly the dynamics of eye blink onsets relative to stimuli timings, we show here that prediction does, in principle, not require visual stimulation, and is also not merely a consequence of the involvement of manual responses during the task. We further show that both the inclusion of manual response to stimuli and elevated task predictability enhance the prediction component reflected in eye blink dynamics, whereas for the latter we experimentally manipulate objective task predictability by adjusting the frequency dependence of the power spectral densities of the series of inter-stimulus time intervals. This allows us finally to explain why, for specific choices of experimental conditions, the generally active and present prediction component involved in attention can become difficult to detect in non-visual, auditory tasks. Conversely, this comes with the important implication that, if tasks aim for elaborating particularly temporal prediction, distributing stimuli over time such that inter-stimulus-intervals conform to a sample of Gaussian noise represents a specifically unfavorable choice.

Patterns of eye blinks are modulated by auditory input in humans.

Previous studies could elaborate a link between attentional processes and eye blinking in both visual and auditory attention tasks. Here we show that this link is active at a fundamental level of perception: presentation of a series of bare sine tones is sufficient to induce a modulation of temporal blink patterns, allowing to determine which series was presented to participants even when they are not required to interactively engage in processing the auditory input. In particular, we monitored eye blinking during an auditory attention task using two series of sine tones, differing in the predictability of the timing of tone onsets. Whereas inter-onset intervals in one tone series corresponded to uncorrelated samples from a normal distribution, they were distributed according to a Gaussian random walk in the other tone series. We find that blink patterns are dynamically modulated by both purely auditory inputs. The magnitude, form, and coherence of the temporal associations between tone onsets and blink events depend strongly on the requirement to respond to the presented stimuli. The predictability of the tone series appears to modulate pre-stimulus blink inhibition given that a response is required. Altogether, these findings suggest eye blink as a readily available, non-invasive behavioral marker for context-sensitive, moment-to-moment allocation of attention.

Wakeful resting and listening to music contrast their effects on verbal long-term memory in dependence on word concreteness.

Wakeful resting and listening to music are powerful means to modulate memory. How these activities affect memory when directly compared has not been tested so far. In two experiments, participants encoded and immediately recalled two word lists followed by either 6 min wakefully resting or 6 min listening to music. The results of Experiment 1 show that both post-encoding conditions have a similar effect on memory after 1 day. In Experiment 2, we explored the possibility that less concrete words, i.e. lower in imageability than in Experiment 1, are differently affected by the two post-encoding conditions. The results of Experiment 2 show that, when words are less concrete, more words are retained after 1 day when encoding is followed by wakeful resting rather than listening to music. These findings indicate that the effects of wakeful resting and listening to music on memory consolidation are moderated by the concreteness of the encoded material.

Dissociative electron attachment to ß-alanine.

A detailed study on dissociative electron attachment (DEA) to ß-alanine (ßA) in the gas phase is presented. Ion yields as a function of the incident electron energy from about 0 to 15 eV have been measured for most of the fragments. As for all α-amino acids, the main reaction corresponds to the loss of a hydrogen atom, although many other fragments have been observed that involved more complex bond cleavages. Threshold energies have been calculated by using the G4(MP2) method for various decomposition reactions. Fragmentation pathways were also investigated to measure metastable decays of the intermediate fragment anion (ßA-H)(-) by using the mass-analyzed ion kinetic energy (MIKE) scan technique. Comparisons with α-alanine and other amino acids are made when relevant.