The Hamiltonian of the V15_{15} Spin System from first-principles Density-Functional Calculations

We report first-principles all-electron density-functional based studies of the electronic structure, magnetic ordering and anisotropy for the V$_{15}$ molecular magnet. From these calculations, we determine a Heisenberg Hamiltonian with four antiferromagnetic and one {\em ferromagnetic} coupling. We perform direct diagonalization to determine the temperature dependence of the susceptibility. This Hamiltonian reproduces the experimentally observed spin $S$=1/2 ground state and low-lying $S$=3/2 excited state. A small anisotropy term is necessary to account for the temperature independent part of the magnetization curve.Comment: 4 pages in RevTeX format + 2 ps-figures, accepted by PRL Feb. 2001 (previous version was an older version of the paper

Magnetic ordering, electronic structure and magnetic anisotropy energy in the high-spin Mn10_{10} single molecule magnet

We report the electronic structure and magnetic ordering of the single molecule magnet [Mn$_{10}$O$_{4}$(2,2'-biphenoxide)$_{4}$Br$_{12}$]$^{4-}$ based on first-principles all-electron density-functional calculations. We find that two of the ten core Mn atoms are coupled antiferromagnetically to the remaining eight, resulting in a ferrimagnetic ground state with total spin S=13. The calculated magnetic anisotropy barrier is found to be 9 K in good agreement with experiment. The presence of the Br anions impact the electronic structure and therefore the magnetic properties of the 10 Mn atoms. However, the electric field due to the negative charges has no significant effect on the magnetic anisotropy.Comment: 4 pages, submitted to PR

Density-functional-based predictions of Raman and IR spectra for small Si clusters

We have used a density-functional-based approach to study the response of silicon clusters to applied electric fields. For the dynamical response, we have calculated the Raman activities and infrared (IR) intensities for all of the vibrational modes of several clusters (SiN with N=3-8, 10, 13, 20, and 21) using the local density approximation (LDA). For the smaller clusters (N=3-8) our results are in good agreement with previous quantum-chemical calculations and experimental measurements, establishing that LDA-based IR and Raman data can be used in conjunction with measured spectra to determine the structure of clusters observed in experiment. To illustrate the potential of the method for larger clusters, we present calculated IR and Raman data for two low-energy isomers of Si10 and for the lowest-energy structure of Si13 found to date. For the static response, we compare our calculated polarizabilities for N=10, 13, 20, and 21 to recent experimental measurements. The calculated results are in rough agreement with experiment, but show less variation with cluster size than the measurements. Taken together, our results show that LDA calculations can offer a powerful means for establishing the structures of experimentally fabricated clusters and nanoscale systems

Vibrational signatures for low-energy intermediate-sized Si clusters

We report low-energy locally stable structures for the clusters Si20 and Si21. The structures were obtained by performing geometry optimizations within the local density approximation. Our calculated binding energies for these clusters are larger than any previously reported for this size regime. To aid in the experimental identification of the structures, we have computed the full vibrational spectra of the clusters, along with the Raman and IR activities of the various modes using a recently developed first-principles technique. These represent, to our knowledge, the first calculations of Raman and IR spectra for Si clusters of this size

Electronic Structure of Superconducting Ba6c60

We report the results of first-principles electronic-structure calculations for superconducting Ba6C60. Unlike the A3C60 superconductors, this new compound shows strong Ba-C hybridization in the valence and conduction regions, mixed covalent/ionic bonding character, partial charge transfer, and insulating zero-gap band structure.Comment: 11 pages + 4 figures (1 appended, others on request), LaTeX with REVTE

DFT calculation of the intermolecular exchange interaction in the magnetic Mn4_4 dimer

The dimeric form of the single-molecule magnet [Mn$_4$O$_3$Cl$_4$(O$_2$CEt)$_3$(py)$_3$]$_2$ recently revealed interesting phenomena: no quantum tunneling at zero field and tunneling before magnetic field reversal. This is attributed to substantial antiferromagnetic exchange interaction between different monomers. The intermolecular exchange interaction, electronic structure and magnetic properties of this molecular magnet are calculated using density-functional theory within generalized-gradient approximation. Calculations are in good agreement with experiment.Comment: 4 page

Hydrogenated and deuterated iron clusters: Infrared spectra and density functional calculations

Iron clusters react sequentially with hydrogen molecules to form multiply hydrogenated products. The increases in cluster ionization potential upon reaction verify that hydrogen chemisorbs dissociatively to form iron cluster–hydride complexes, FenHm. At low source temperatures, the cluster–hydride complexes take up additional hydrogen molecules which are shown to be physisorbed onto the underlying FenHm complexes to form FenHm(H2)p species. The infrared spectra of FenHm and FenDm (n = 9–20) were obtained by the photodissociation action spectroscopic method in which depletion of the FenHm(H2)p and FenDm(D2)p species was the signature of absorption. The spectra, recorded in the 885–1090 cm−1 region, consist of several overlapping bands, each approximately 20 cm−1 in width. The dissimilarity of each FenHm(H2)p spectrum with the corresponding FenDm(D2)p spectrum indicates that the carrier involves hydrogen and is not merely due to absorption by the underlying iron cluster. Density functional calculations were performed on model complexes, Fe13H14 and Fe13D14, the iron portion of which was assumed to have Th symmetry. The infrared-active vibrational frequencies involving hydrogen bending and deuterium stretching are predicted to lie within the experimental frequency range of the experiment, well removed from the skeletal modes of the underlying iron cluster. The complexity of the observed spectra as compared to simulations based on the assumed (high-symmetry) model imply that the experimentally produced complexes possess low symmetry

Photo-excitation of a light-harvesting supra-molecular triad: a Time-Dependent DFT study

We present the first time-dependent density-functional theory (TDDFT) calculation on a light harvesting triad carotenoid-diaryl-porphyrin-C60. Besides the numerical challenge that the ab initio study of the electronic structure of such a large system presents, we show that TDDFT is able to provide an accurate description of the excited state properties of the system. In particular we calculate the photo-absorption spectrum of the supra-molecular assembly, and we provide an interpretation of the photo-excitation mechanism in terms of the properties of the component moieties. The spectrum is in good agreement with experimental data, and provides useful insight on the photo-induced charge transfer mechanism which characterizes the system.Comment: Accepted for publication on JPC, March 09th 200

Controlled auxin biosynthesis and transport are important for developmental decisions in the early diverging land plant Physcomitrella patens

The aim of this thesis was to increase our understanding of the importance of the plant hormone auxin in land plant evolution. The role of a number of auxin regulatory network components in developmental decisions during the haploid phase of the life cycle of the model moss Physcomitrella patens, which belongs to the early diverging bryophyte group of land plants, was investigated. We show that the role of SHI/STY transcriptional activators in the regulation of auxin biosynthesis rates in seed plants is conserved in moss. The amount and rates of auxin synthesis are reduced in PpSHI knockout mutants, defects in these mutants can be mimicked by reducing active auxin in the PpSHI expression domain, and several moss homologues of YUC and TAA1/TAR genes, which encode the main auxin biosynthesis enzymes in seed plants, were activated in moss when PpSHI2 was transiently expressed. Our data reveal that these moss YUC and TAA1/TAR genes can induce auxin biosynthesis, and that their expression domains largely overlap with that of the two PpSHIs in certain stages of the moss life cycle. PpSHI2 also directly or indirectly activates homologues of genes involved in polar auxin transport (PAT) in seed plants, PpPINA, PpPINB and PpLAXB. We show that the auxin efflux function of PIN proteins have been conserved during the evolution of land plants, and that they, together with the PpSHI auxin biosynthesis regulators, are important for determining developmentally regulated decisions, such as the switch between two cell types of the filamentous stage in moss. In addition, PIN-mediated distribution of auxin synthesised in the leaves plays an important role in determining a developmentally regulated wave of cell expansion. PpSHI regulated local auxin biosynthesis is crucial for several steps in reproductive organ development, such as egg cell maturation, clearance of a canal to the egg cavity, as well as apical opening of both male and female reproductive organs allowing sperm release and entrance into the egg cavity. If polar auxin transport plays a role during these stages remains to be studied. This demonstrates that regulated distribution of auxin was operational in cell-fate decisions already in the early land plants, and that auxin has played a key role in the evolution of complex land plant structures