Unraveling structures of protection ligands on gold nanoparticle Au68(SH)32

New low-energy atomic structures of the thiolate-protected gold nanoparticle Au68(SH)32 are uncovered, where the atomic positions of the Au atoms are taken from the recent single-particle transmission electron microscopy measurement by Kornberg and co-workers, whereas the pattern of thiolate ligands on the gold core is attained on the basis of the generic formulation (or rule) of the “divide and protect” concept. Four distinct low-energy isomers, Iso1 to Iso4, whose structures all satisfy the generic formulation, are predicted. Density-functional theory optimization indicates that the four isomers are all lower in energy by 3 to 4 eV than the state-of-the-art low-energy isomer reported. Further analysis of the optimized structures of Au68(SH)32 shows that the structure of gold core in Iso1 to Iso4 is consistent with the experiment, whereas the positions of a few Au atoms at the surface of gold core are different. The computed optical absorption spectra of the four isomers are consistent with the measured spectrum. Computation of catalytic properties of Au68(SH)32 toward CO oxidation suggests that the magic number cluster can be a stand-alone nanoscale catalyst for future catalytic applications.

The search for the most stable structures of silicon–carbon monolayer compounds

The most stable structures of two-dimensional (2D) silicon–carbon monolayer compounds with different stoichiometric compositions (i.e., Si : C ratio = 2 : 3, 1 : 3 and 1 : 4) are predicted for the first time based on the particle-swarm optimization (PSO) technique combined with density functional theory optimization.

A study of the low-lying singlet and triplet electronic states of chlorophyll A and B

Chlorophylls have been extensively investigated both experimentally and theoretically owing to the fact that they are essential for photosynthesis. We have studied two forms of chlorophyll, chlorophyll a and chlorophyll b, by means of density functional theory. Optimization of S0, S1 and T1 states was performed with the B3-LYP functional. The computed fluorescence lifetimes show good agreement with the available experimental data. The electronic adiabatic energies of S1 and T1 states are 2.09/2.12 and 1.19/1.29 eV for chlorophyll a and chlorophyll b respectively. We discussed the implications of this results on the triplet formation. Also, the calculated vertical ionization potentials shows good agreement with the experimental results.

Wechselwirkungen in Molekülkristallen, 166 [1, 2]. Polyiod-Moleküle I2C=CI2, (IC)4S, (IC)4NH, (IC)4N-CH3 und HCI3: Strukturbestimmung nach Kristallzüchtung oder durch Dichtefunktionaltheorie-Berechnung / Interaction in Molecular Crystals, 166 [1, 2], Polyiodo Molecules I2C=CI2, (IC)4S, (IC)4 NH, (IC)4N-CH and HCI3: Structure Determination Following Crystallization or by Density Functional Theory Calculation

The structures of tri-and tetraiodo-substituted carbon compounds are determined either expe­rimentally by X-Ray Structure Analysis or, because crystallization of tetraiodothiophene could not be achieved, approximated by Density Functional Theory optimization of structural data from a donor/acceptor complex. The structures show noteworthy details such as a second po­lymorph of tetraiodoethene crystallized by sublimation or herringbone crystal packing patterns of tetraiodopyrrole derivatives. All molecular geometries are discussed and compared based on relativistic density functional theory calculations with 6 -31G* basis sets including iodine pseudopotentials. They reproduce even finer structural details due to van der Waals repulsion of the bulky iodo substituents. Natural Bond Orbital (NBO) charge distributions suggest positive partial charges at all iodine centers with the strongest polarization Cδ㊀ → Iδ㊉ in HCI3, which contains well over 97% iodine.