Modulation of the local density of states within the dd-density wave theory in the underdoped cuprates

The low temperature scanning tunneling microscopy spectra in the underdoped regime is analyzed from the perspective of coexisting $d$-density wave and d-wave superconducting states. The calculations are carried out in the presence of a low concentration of unitary impurities and within the framework of the fully self-consistent Bogoliubov-de Gennes theory, which allows local modulations of the magnitude of the order parameters in response to the impurities. Our theory captures the essential aspects of the experiments in the underdoped BSCCO at very low temperatures.Comment: 4 pages, 4 eps figures, RevTex4. New added material as well as reference

OsB9 −: An Aromatic Osmium-Centered Monocyclic Boron Ring

Transition-metal-centered monocyclic boron wheels are important candidates in the family of planar hypercoordinate species that show intriguing structure, stability and bonding situation. Through the detailed potential energy surface explorations of MB9 − (M Fe, Ru, Os) clusters, we introduce herein OsB9 − to be a new member in the transition-metalcentered borometallic molecular wheel gallery. Previously, FeB9 − and RuB9 − clusters were detected by photoelectron spectroscopy and the structures were reported to have singlet D9h symmetry. Our present results show that the global minimum for FeB9 − has a molecular wheel-like structure in triplet spin state with Cs symmetry, whereas its heavier homologues are singlet molecular wheels with D9h symmetry. Chemical bonding analyses show that RuB9 − and OsB9 − display a similar type of electronic structure, where the dual σ + π aromaticity, originated from three delocalized σ bonds and three delocalized π bonds, accounts for highly stable borometallic molecular wheels

B3Al4+ : A Three-Dimensional Molecular Reuleaux Triangle

We systematically explore the potential energy surface of the B3Al4+ combination of atoms. The putative global minimum corresponds to a structure formed by an Al-4 square facing a B-3 triangle. Interestingly, the dynamical behavior can be described as a Reuleaux molecular triangle since it involves the rotation of the B-3 triangle at the top of the Al-4 square. The molecular dynamics simulations, corroborating with the very small rotational barriers of the B-3 triangle, show its nearly free rotation on the Al-4 ring, confirming the fluxional character of the cluster. Moreover, while the chemical bonding analysis suggests that the multicenter interaction between the two fragments determines its fluxionality, the magnetic response analysis reveals this cluster as a true and fully three-dimensional aromatic system.Peer reviewe

B3Al4+: A Three-Dimensional Molecular Reuleaux Triangle

We systematically explore the potential energy surface of the B3Al4+ combination of atoms. The putative global minimum corresponds to a structure formed by an Al4 square facing a B3 triangle. Interestingly, the dynamical behavior can be described as a Reuleaux molecular triangle since it involves the rotation of the B3 triangle at the top of the Al4 square. The molecular dynamics simulations, corroborating with the very small rotational barriers of the B3 triangle, show its nearly free rotation on the Al4 ring, confirming the fluxional character of the cluster. Moreover, while the chemical bonding analysis suggests that the multicenter interaction between the two fragments determines its fluxionality, the magnetic response analysis reveals this cluster as a true and fully three-dimensional aromatic system

d-d Dative Bonding Between Iron and the Alkaline-Earth Metals Calcium, Strontium, and Barium

Double deprotonation of the diamine 1,1 '-(tBuCH(2)NH)-ferrocene (1-H-2) by alkaline-earth (Ae) or Eu(II)metal reagents gave the complexes1-Ae (Ae=Mg, Ca, Sr, Ba) and1-Eu.1-Mg crystallized as a monomer while the heavier complexes crystallized as dimers. The Fe...Mg distance in1-Mg is too long for a bonding interaction, but short Fe...Ae distances in1-Ca,1-Sr, and1-Ba clearly support intramolecular Fe...Ae bonding. Further evidence for interactions is provided by a tilting of the Cp rings and the related(1)H NMR chemical-shift difference between the Cp alpha and beta protons. While electrochemical studies are complicated by complex decomposition, UV/Vis spectral features of the complexes support Fe -> Ae dative bonding. A comprehensive bonding analysis of all1-Ae complexes shows that the heavier species1-Ca,1-Sr, and1-Ba possess genuine Fe -> Ae bonds which involve vacant d-orbitals of the alkaline-earth atoms and partially filled d-orbitals on Fe. In1-Mg, a weak Fe -> Mg donation into vacant p-orbitals of the Mg atom is observed

Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand

The formation of isolable monatomic BiI complexes and BiII radical species is challenging due to the pronounced reducing nature of metallic bismuth. Here, we report a convenient strategy to tame BiI and BiII atoms by taking advantage of the redox noninnocent character of a new chelating bis(germylene) ligand. The remarkably stable novel BiI cation complex 4, supported by the new bis(iminophosphonamido-germylene)xanthene ligand [(P)GeII(Xant)GeII(P)] 1, [(P)GeII(Xant)GeII(P) = Ph2P(NtBu)2GeII(Xant)GeII(NtBu)2PPh2, Xant = 9,9-dimethyl-xanthene-4,5-diyl], was synthesized by a two-electron reduction of the cationic BiIIII2 precursor complex 3 with cobaltocene (Cp2Co) in a molar ratio of 1:2. Notably, owing to the redox noninnocent character of the germylene moieties, the positive charge of BiI cation 4 migrates to one of the Ge atoms in the bis(germylene) ligand, giving rise to a germylium(germylene) BiI complex as suggested by DFT calculations and X-ray photoelectron spectroscopy (XPS). Likewise, migration of the positive charge of the BiIIII2 cation of 3 results in a bis(germylium)BiIIII2 complex. The delocalization of the positive charge in the ligand engenders a much higher stability of the BiI cation 4 in comparison to an isoelectronic two-coordinate Pb0 analogue (plumbylone; decomposition below −30 °C). Interestingly, 4[BArF] undergoes a reversible single-electron transfer (SET) reaction (oxidation) to afford the isolable BiII radical complex 5 in 5[BArF]2. According to electron paramagnetic resonance (EPR) spectroscopy, the unpaired electron predominantly resides at the BiII atom. Extending the redox reactivity of 4[OTf] employing AgOTf and MeOTf affords BiIII(OTf)2 complex 7 and BiIIIMe complex 8, respectively, demonstrating the high nucleophilic character of BiI cation 4

Synthesis of a rhodium(III) dinitrogen complex using a calix[4]arene-based diphosphine ligand

The synthesis and characterisation of the rhodium(III) dinitrogen complex [Rh(2,2’-biphenyl)(CxP2)(N2)]+ are described, where CxP2 is a trans-spanning calix[4]arene-based diphosphine and the dinitrogen ligand is projected into the cavity of the macrocycle