Physics

We investigate the peptide AcPheAla5LysH+, a model system for studying helix formation in the gas phase, in order to fully understand the forces that stabilize the helical structure. In particular, we address the question of whether the local fixation of the positive charge at the peptide's C-terminus is a prerequisite for forming helices by replacing the protonated C-terminal Lys residue by Ala and a sodium cation. The combination of gas-phase vibrational spectroscopy of cryogenically cooled ions with molecular simulations based on density-functional theory (DFT) allows for detailed structure elucidation. For sodiated AcPheAla6, we find globular rather than helical structures, as the mobile positive charge strongly interacts with the peptide backbone and disrupts secondary structure formation. Interestingly, the global minimum structure from simulation is not present in the experiment. We interpret that this is due to high barriers involved in re-arranging the peptide-cation interaction that ultimately result in kinetically trapped structures being observed in the experiment.

A knife edge for shaping a molecular beam is described to improve the spatial separation of the species in a molecular beam by the electrostatic deflector. The spatial separation of different molecular species from each other as well as from atomic seed gas is improved. The column density of the selected molecular-beam part in the interaction zone, which corresponds to higher signal rates, was enhanced by a factor of 1.5, limited by the virtual source size of the molecular beam.

We investigate from a practitioner's point of view the computation of the ionization potential (IP) within density functional theory (DFT). DFT with (semi-)local energy-density functionals is plagued by a self-interaction error which hampers the computation of IP from the single-particle energy of the highest occupied molecular orbital (HOMO). The problem may be cured by a self interaction correction (SIC) for which there exist various approximate treatments. We compare the performance of the SIC proposed by Perdew and Zunger with the very simple average-density SIC (ADSIC) for a large variety of atoms and molecules up to larger systems as carbon rings and chains. Both approaches to SIC provide a large improvement to the quality of the IP if calculated from the HOMO level. The surprising result is that the simple ADSIC performs even better than the original Perdew-Zunger SIC (PZSIC) in the majority of the studied cases.

In this work we use magnetic deflection of V, Nb, and Ta atomic clusters to measure their magnetic moments. While only a few of the clusters show weak magnetism, all odd-numbered clusters deflect due to the presence of a single unpaired electron. Surprisingly, for majority of V and Nb clusters an atomic-like behavior is found, which is a direct indication of the absence of spin-lattice interaction. This is in agreement with Kramers degeneracy theorem for systems with a half-integer spin. This purely quantum phenomenon is surprisingly observed for large systems of more than 20 atoms, and also indicates various quantum relaxation processes, via Raman two-phonon and Orbach high-spin mechanisms. In heavier, Ta clusters, the relaxation is always present, probably due to larger masses and thus lower phonon energies, as well as increased spin-orbit coupling.

Besides buckminsterfullerene (C60), other fullerenes and their derivatives may also reside in space. In this work, we study the formation and photo-dissociation processes of astronomically relevant fullerene/anthracene (C14H10) cluster cations in the gas phase. Experiments are carried out using a quadrupole ion trap (QIT) in combination with time-of-flight (TOF) mass spectrometry. The results show that fullerene (C60, and C70)/anthracene (i.e., [(C14H10)nC60]+ and [(C14H10)nC70]+), fullerene (C56 and C58)/anthracene (i.e., [(C14H10)nC56]+ and [(C14H10)nC58]+) and fullerene (C66 and C68)/anthracene (i.e., [(C14H10)nC66]+ and [(C14H10)nC68]+) cluster cations, are formed in the gas phase through an ion-molecule reaction pathway. With irradiation, all the fullerene/anthracene cluster cations dissociate into mono − anthracene and fullerene species without dehydrogenation. The structure of newly formed fullerene/anthracene cluster cations and the bonding energy for these reaction pathways are investigated with quantum chemistry calculations. Our results provide a growth route towards large fullerene derivatives in a bottom-up process and insight in their photo-evolution behavior in the ISM, and clearly, when conditions are favorable, fullerene/PAH clusters can form efficiently. In addition, these clusters (from 80 to 154 atoms or ~ 2 nm in size) offer a good model for understanding the physical-chemical processes involved in the formation and evolution of carbon dust grains in space, and provide candidates of interest for the DIBs that could motivate spectroscopic studies.

Ethanediol is one of the largest complex organic molecules detected in space thus far. It has been found in different types of molecular clouds. The two propanediol isomers are the next larger diols. Hence, they are viable candidates to be searched for in space. We wish to provide sufficiently large and accurate sets of spectroscopic parameters of 1,2-propanediol to facilitate searches for this molecule at millimeter and longer submillimeter wavelengths. We recorded rotational spectra of 1,2-propanediol in three wide frequency windows between 38 and 400~GHz. We made extensive assignments for the three lowest energy conformers to yield spectroscopic parameters up to eighth order of angular momentum. Our present data will be helpful for identifying 1,2-propanediol at moderate submillimeter or longer wavelengths with radio telescope arrays such as ALMA, NOEMA, or EVLA. In particular, its detection with ALMA in sources, in which ethanediol was detected, appears to be promising.

The formation and evolution mechanism of fullerenes in the planetary nebula or in the interstellar medium are still not understood. Here we present the study on the cluster formation and the relative reactivity of fullerene cations (from smaller to larger, C 44 to C 70 ) with anthracene molecule (C 14 H 10 ). The experiment is performed in the apparatus that combines a quadrupole ion trap with a time-of-flight mass spectrometer. By using a 355 nm laser beam to irradiate the trapped fullerenes cations (C 60 + or C 70 + ), smaller fullerene cations C (60−2n) + , n=1-8 or C (70−2m) + , m=1-11 are generated, respectively. Then reacting with anthracene molecules, series of fullerene/anthracene cluster cations are newly formed (e.g., (C 14 H 10 )C (60−2n) + , n=1-8 and (C 14 H 10 )C (70−2m) + , m=1-11), and slight difference of the reactivity within the smaller fullerene cations are observed. Nevertheless, smaller fullerenes show obviously higher reactivity when comparing to fullerene C 60 + and C 70 + . A successive loss of C 2 fragments mechanism is suggested to account for the formation of smaller fullerene cations, which then undergo addition reaction with anthracene molecules to form the fullerene-anthracene cluster cations. It is found that the higher laser energy and longer irradiation time are key factors that affect the formation of smaller fullerene cations. This may indicate that in the strong radiation field environment (such as photon-dominated regions) in space, fullerenes are expected to follow the top-down evolution route, and then form small grain dust (e.g., clusters) through collision reaction with co-existing molecules, here, smaller PAHs.

The size dependent electronic structure and separate spin and orbital magnetic moments of free Co + n ( n=4-9 ) cluster ions have been investigated by x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap. A very large orbital magnetic moment of 1.4±0.1 μ B per atom was determined for Co + 5 , which is one order of magnitude larger than in the bulk metal. Large orbital magnetic moments per atom of ≈1 μ B were also determined for Co + 4 , Co + 6 , and Co + 8 . The orbital contribution to the total magnetic moment shows a non-monotonic cluster size dependence: The orbital contribution increases from a local minimum at n=2 to a local maximum at n=5 and then decreases with increasing cluster size. The 3d spin magnetic moment per atom is nearly constant and is solely defined by the number of 3d holes which shows that the 3d majority spin states are fully occupied, that is, 3d hole spin polarization is 100%.

We report the linear optical absorption spectra of aluminum clusters Al n (n=2--5) involving valence transitions, computed using the large-scale all-electron configuration interaction (CI) methodology. Several low-lying isomers of each cluster were considered, and their geometries were optimized at the coupled-cluster singles doubles (CCSD) level of theory. With these optimized ground-state geometries, excited states of different clusters were computed using the multi-reference singles-doubles configuration-interaction (MRSDCI) approach, which includes electron correlation effects at a sophisticated level. These CI wave functions were used to compute the transition dipole matrix elements connecting the ground and various excited states of different clusters, and thus their photoabsorption spectra. The convergence of our results with respect to the basis sets, and the size of the CI expansion, was carefully examined. Our results were found to be significantly different as compared to those obtained using time-dependent density functional theory (TDDFT) [Deshpande \textit{et al. Phys. Rev. B}, 2003, \textbf{68}, 035428]. When compared to available experimental data for the isomers of Al 2 and Al 3 , our results are in very good agreement as far as important peak positions are concerned. The contribution of configurations to many body wavefunction of various excited states suggests that in most cases optical excitations involved are collective, and plasmonic in nature.

We report on an experimental and theoretical study of the ionization-fragmentation dynamics of argon dimers in intense few-cycle laser pulses with a tagged carrier-envelope phase. We find that a field-driven electron transfer process from one argon atom across the system boundary to the other argon atom triggers sub-cycle electron-electron interaction dynamics in the neighboring atom. This attosecond electron-transfer process between distant entities and its implications manifest themselves as a distinct phase-shift between the measured asymmetry of electron emission curves of the Ar + + Ar 2+ and Ar 2+ + Ar 2+ fragmentation channels. Our work discloses a strong-field route to controlling the dynamics in molecular compounds through the excitation of electronic dynamics on a distant molecule by driving inter-molecular electron-transfer processes.