Quantum studies of H atom trapping on a graphite surface

The trapping and sticking of H and D atoms on the graphite (0001) surface is examined, over the energy range of 0.1-0.9 eV. For hydrogen to chemisorb onto graphite, the bonding carbon must pucker out of the surface plane by several tenths of an angstrom. A quantum approach in which both the hydrogen and the bonding carbon atoms can move is used to model the trapping, and a potential energy surface based on density functional theory calculations is employed. It is found, for energies not too far above the 0.2 eV barrier to chemisorption that a significant fraction of the incident H or D atoms can trap. The forces on the bonding carbon are large, and it can reconstruct within 50 fs or so. After about 100 fs, most of the trapped H atoms scatter back into the gas phase, but the 5%-10% that remain can have lifetimes on the order of a picosecond or more. Calculations of the resonance eigenstates and lifetimes confirm this. An additional lattice degree of freedom is included quantum mechanically and is shown to significantly increase the amount of H that remains trapped after 1 ps. Further increasing the incident energy destabilizes the trapped state, leading to less H remaining trapped at long times. We estimate that for a full dissipative bath, the sticking probabilities should be on the order of 0.1.     

Rapid assembly of the polyhydroxylated beta-amino acid constituents of microsclerodermins C, D, and E

A very short and efficient synthesis of protected derivatives of APTO and AETD, the complex polyhydroxylated beta-amino acid residues present in microsclerodermins C, D, and E, is described. The targets are obtained in only five steps, in 23% and 16% overall yields, respectively. The key transformation involves the completely diastereoselective two-carbon homologation of appropriately selected intermediate chiral sulfinimines.     

Electron photodetachment from gas phase peptide dianions. Relation with optical absorption properties

Electron detachment from peptide dianions is studied as a function of the laser wavelength. The first step for the detachment is a resonant electronic excitation of the dianions. Electronic excitation spectra are reported for three peptides, including gramicidin. A comparative study of the detachment yield for 13 peptides was performed at 260 nm and at 220 nm. At 260 nm, the detachment yield is mainly driven by the sum of the absorption coefficients of the aromatic amino acids that are contained in the peptide. At 220 nm, no direct relation is observed between the electron photodetachement yields and the sum of absorption efficiencies. At this wavelength, the sequence and the structure of the peptide may have an influence on the photodetachment process.     

Copper‐Rich Thermoelectric Sulfides: Size‐Mismatch Effect and Chemical Disorder in the [TS4]Cu6 Complexes of Cu26T2Ge6S32 (T=Cr,Mo, W) Colusites

Herein, we investigate the Mo and W substitution for Cr in synthetic colusite, Cu₂₆Cr₂Ge₆S₃₂. Primarily, we elucidate the origin of extremely low electrical resistivity which does not compromise the Seebeck coefficient and leads to outstanding power factors of 1.94 mW m^?1 K^?2 at 700 K in Cu₂₆Cr₂Ge₆S₃₂. We demonstrate that the abnormally long iono‐covalent T–S bonds competing with short metallic Cu–T interactions govern the electronic transport properties of the conductive “Cu₂₆S₃₂” framework. We address the key role of the cationic size‐mismatch at the core of the mixed tetrahedral–octahedral complex over the transport properties. Two essential effects are identified: 1) only the tetrahedra that are directly bonded to the [TS₄]Cu₆ complex are significantly distorted upon substitution and 2) the major contribution to the disorder is localized at the central position of the mixed tetrahedral–octahedral complex, and is maximized for x=1, i.e. for the highest cationic size‐variance, σ².     

Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis,Separation, Structural and DFT Studies of [Re6−xMoxSe8(CN)6]n−

Influence of the metal core composition and geometry on the structure, spectroscopic properties and redox potentials was investigated for the first time for heterometallic (Re/Mo)₆ octahedral clusters. The discrete anionic clusters [Re_6-xMo_xSe₈(CN)₆]ⁿ⁻ (x=2, 3; n=4, 5) were obtained as individual salts. Their isomeric composition and bond-length distribution were inspected using a combination of single-crystal X-ray structure analysis, NMR, EXAFS, and DFT calculations.     

Experimental and theoretical study of density,potential, and current structures of a helium plasma in front of an radio frequency antenna tilted with respect to the magnetic field lines

Potential and density structures in the vicinity of an radio frequency (RF) electrode/antenna in a magnetized plasma are investigated using an RF-compensated cylindrical Langmuir probe. These measurements were performed in the ALINE plasma device in which only electrons can be considered well magnetized. Very precise 2-D maps of the plasma parameters are drawn thanks to a 3-D automatic manipulator on which the probe is mounted. The effect of the tilted magnetic angle between the RF-biased surface and the magnetic lines is also studied thanks to a tilting electrode. Comparison of several simplistic models with the experiments proved the reliability of simple Langmuir probe measurements in such an RF and magnetized environment (space potential vs. tilting angle of the antenna with respect to magnetic field lines and recovery of the floating potential structure using measured currents). A fluid model based on total current density and ion diffusion equations over the biased flux tube provides the same density structures in front of the electrode as the measurements. Those density structures display a “bunny ears” shape and can be explained using transverse RF and collisional current behaviour: In front of the antenna, the transverse ion currents deplete the magnetized flux tube, while at the edge of the biased flux tube, the same currents increase the density.     

Electron photodetachment of trapped doubly deprotonated angiotensin peptides. UV spectroscopy and radical recombination

Trapped doubly deprotonated peptides are subjected to electron detachment when irradiated by a UV light. Electron photodetachment experiments as a function of the laser wavelength and laser fluence have been performed on two variants of angiotensin. The electron detachment yield was used to monitor the excited electronic spectrum of the trapped ions. Furthermore, the electron loss leads to the formation of radical ions. The radical recombination after collision activation is discussed.     

Calculating the distribution of transferred hyperfine fields at the Sn site in tetragonal CeScSi-type RMgSn compounds

We present a simple model based on an isotropic transferred hyperfine field to calculate the transferred hyperfine field distribution at the Sn site of the antiferromagnetic CeScSi-type RMgSn compounds. The calculations correctly reproduce the main features observed in NdMgSn, TbMgSn, DyMgSn, HoMgSn, and ErMgSn. The transferred hyperfine field distributions are remarkably sensitive to the complex magnetic structures in the RMgSn compounds, and can be used to discriminate between competing magnetic structure models.