Search results for "bond"
showing 10 items of 3527 documents
Alternative single-reference coupled cluster approaches for multireference problems: the simpler, the better.
2011
We report a general implementation of alternative formulations of single-reference coupled cluster theory (extended, unitary, and variational) with arbitrary-order truncation of the cluster operator. These methods are applied to compute the energy of Ne and the equilibrium properties of HF and C(2). Potential energy curves for the dissociation of HF and the BeH(2) model computed with the extended, variational, and unitary coupled cluster approaches are compared to those obtained from the multireference coupled cluster approach of Mukherjee et al. [J. Chem. Phys. 110, 6171 (1999)] and the internally contracted multireference coupled cluster approach [F. A. Evangelista and J. Gauss, J. Chem. …
G2(MP2) Investigation of Alane-[X(CH3)3]- (X = C, Si, and Ge) and Alane-Y(CH3)3 (Y = N, P, and As) Interactions
2001
Alane-[X(CH3)3]- (X = C, Si, and Ge) and alane-Y(CH3)3 (Y = N, P, and As) have been investigated as donor−acceptor complex types at the G2(MP2) level of theory. The results show that the anionic complexes are more stable than the neutral ones. They show also that this stability decreases when going from carbon to germanium for [H3AlX(CH3)3]- complexes and from nitrogen to arsenic for H3AlY(CH3)3 complexes. The interaction diagrams prove that the evolution of complexation energy depends on the coordination mode. In fact, it is a result of two interaction types: interaction between “a1” symmetry fragment molecular orbital (stabilizing) and interactions between “e” symmetry fragment molecular…
Structure of Dioxygen Binding Xerogels Incorporating Cyclams Complexed with CuCl2 Salts
2005
X-ray absorption/emission spectroscopies were combined in order to elucidate how hybrid xerogels complexed with CuCl2 could bind reversibly O2. Difference EXAFS analyses at the Cu K-edge revealed the existence of binuclear structures with long Cu...Cu distances, i.e. RCu–Cu ≈ 3.98 A and 3.87 A for the oxygenated and oxygen-free xerogels. In oxygenated xerogels, dioxygen would bridge two Cu atoms in a μ-η1 : η1 peroxo-like conformation. The Cu-O signal found at short distance (RCu−O1 = 1.85 ± 0.01 A) is fully consistent with 40% of O2 molecules being chemisorbed per Cu site. In oxygen-free xerogels, Cl K-edge EXAFS revealed the presence of CuI sites with short Cl-Cu bond lengths (RCl−Cu = 2.…
Neutron diffraction studies of structural and magnetic properties of niobium doped cobaltites.
2009
Neutron powder diffraction studies of the structural and magnetic properties of the La(1-x)Sr(x)Nb(y)Co(1-y)O(3) solid solutions (x = 0.2, 0.5; y = 0, 0.075, 0.1) have been performed. Substitution of Co(2+) by Nb(5+) prevents the formation of Co(4+) and leads to stabilization of the Co(3+) ions in the high- or intermediate-spin state. This is accompanied by the significant change of the Co-O bond length as well as Co-O-Co bond angle in the CoO(6) octahedron. The obtained data are in agreement with the negative sign of the magnetic exchange interactions Co(3+)-O-Co(3+) in a relatively wide range of the Co-O-Co bond angles. Diamagnetic dilution by the niobium ions prevents long-range magnetic…
Electronic Properties of Mixed-Valence Manganates: The Role of Mn Substitutional Defects
2002
Single-phase perovskites in the solid solution series La0.7+yA0.3-yMn1-xMxO3 (with 0.00 ≤ x ≤ 0.10; A = Sr2+, M = Cu2+, Zn2+, Sc3+, Cr3+, Co3+, and Ga3+; A = Ba2+, M = Cu2+, Zn2+, and Sc3+) have been prepared via the acetic acid solutions freeze-drying method. This soft procedure makes possible strict stoichiometric control, and the synthetic variables allow one to maintain a constant proportion of Mn4+ (ca. 32%) in the 47 compounds prepared. In this way, the concentration of cationic vacancies at A and B sites is practically negligible in all cases. X-ray powder diffraction patterns corresponding to the 47 compounds have been completely indexed with rhombohedral perovskite cells. The cryst…
Bis(dimethylammonium) pentachloroantimonate(III), on the deformation of the octahedral coordination of Sb III
1998
The structure of the title compound, [NH2(CH3)2]2SbCl5, was determined at 295 and 85 K. It consists of polymeric (SbCl52−)n chains composed of deformed SbCl63− octahedra connected by corners and dimethylammonium cations. The temperature dependence of the Sb–Cl bond lengths is discussed. It is argued that the deformation of the octahedral coordination of the SbIII atom is caused by electrostatic interaction/hydrogen bonds.
Variable-temperature X-ray crystal structure determinations of {Fe[tren(6-Mepy)3]}(ClO4)2and {Zn[tren(6-Mepy)3]}(ClO4)2compounds: correlation of the …
2007
Variable-temperature X-ray crystal structure determinations (80–330 K) on compounds {Fe[tren(6-Mepy)3]}(ClO4)2(1-Fe) {tren(6-Mepy)3is tris[3-aza-4-(6-methyl-2-pyridyl)but-3-enyl]amine} and {Zn[tren(6-Mepy)3]}(ClO4)2(1-Zn) {tren(6-Mepy)3is tris[3-aza-4-(6-methyl-2-pyridyl)but-3-enyl]amine} were carried out together with a detailed analysis of the unit-cell volume and parameters in the spin transition region for (1-Fe). Both compounds crystallize in the monoclinic system and retained the space groupP21/cat all measured temperatures. The Fe and Zn atoms are surrounded by six N atoms belonging to imine groups and pyridine groups of the trifurcated ligand, adopting a pseudo-octahedral symmetry. …
Relativistic coupled cluster calculations of the electronic structure of KrH+, XeH+ and RnH+
2012
Potential energy curves of NgH+ cations (Ng = Kr, Xe, Rn) were obtained by using four-component relativistic CCSD(T) coupled cluster calculations. Dissociation energies, equilibrium bond lengths, electronic properties, such as dipole moments and electric field gradients at the nuclei, and the related spectroscopic parameters of the electronic ground state have been determined. The results obtained for KrH+ and XeH+ are in good agreement with available experimental data, while those for RnH+ have been determined for the first time at this level of theory.
On the geometry of the HO3 radical
2008
Abstract We discuss the equilibrium structure of the hydrogen trioxy radical (HO3). The CCSD(T) geometry at the approximate basis set limit, in conjunction with the geometry obtained using the CCSDT method and a moderate basis set, suggests an equilibrium HO–OO bond length of approximately 1.59 A.
High-pressure x-ray absorption study of GaTe including polarization
2000
The evolution of the local structure in GaTe under pressure is studied by x-ray absorption spectroscopy experiments at the Ga K-edge (10.368 keV) on oriented single crystals. Taking advantage of the linearly polarized character of synchrotron radiation, the pressure evolution of both the Ga-Te and the in-plane Ga-Ga bond lengths could be determined, in spite of the small amplitude of the latter. Our measurements show that both distances are much less compressible than what could be inferred from the bulk compressibility, which evidences a strong variation of Ga-Ga-Te and Te-Ga-Te angles under pressure. The Te-Te intralayer distance perpendicular to the layers is observed to increase with in…