Theoretical Characterization (theoretical + characterization)

Distribution by Scientific Domains

Selected Abstracts

Cubane-Like Bismuth-Iron Cluster: Synthesis, X-ray Crystal Structure and Theoretical Characterization of the [Bi4Fe8(CO)28]4, Anion

Kirill Yu.
Abstract The reaction of cyclo -Bi4[Si(SiMe3)3]4 (1) with Na2[Fe(CO)4] in the presence of nBu4NCl leads to the formation of the cage compound [nBu4N]4[Bi4Fe8(CO)28] (2). According to X-ray single-crystal structure analysis, the faces of the tetrahedral Bi4 core are capped by Fe(CO)3 moieties in a ,3 fashion to give a cubanoid Bi4Fe4 framework. The four Fe(CO)4 fragments are ,1 -coordinated to bismuth, each. With 12 skeletal electron pairs the [Bi4Fe8(CO)28]4, anion (2a) is a Bi4Fe4 cubane. The negative charge is localized within cluster 2a according to the NBO analysis of its derivatives. The strength of metal,ligand interactions Bi,,3 -Fe(CO)3 is responsible for the size of the cluster's cubic core. NICS computations at the cage centers of considered molecules show that 2a has paratropic character, whereas removal of four ,1 -Fe(CO)4 fragments from latter causes spherical aromaticity of the modified clusters [Bi4Fe4(CO)12]4, (2aa) and [Bi4Fe4(CO)12]2+ (2ab), mediated by a Bi4 cluster , orbital. [source]

ChemInform Abstract: Experimental Detection and Theoretical Characterization of Germanium-Doped Lithium Clusters LinGe (n = 1,7).

CHEMINFORM, Issue 44 2009
Vu Thi Ngan
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]

Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu2O2 Models

CHEMINFORM, Issue 1 2007
Christopher J. Cramer
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source]

Theoretical Characterization of Charge Transport in One-Dimensional Collinear Arrays of Organic Conjugated Molecules

CHEMPHYSCHEM, Issue 5 2010
Lucas Viani
Abstract A great deal of interest has recently focused on host,guest systems consisting of one-dimensional collinear arrays of conjugated molecules encapsulated in the channels of organic or inorganic matrices. Such architectures allow for controlled charge and energy migration processes between the interacting guest molecules and are thus attractive in the field of organic electronics. In this context, we characterize here at a quantum-chemical level the molecular parameters governing charge transport in the hopping regime in 1D arrays built with different types of molecules. We investigate the influence of several parameters (such as the symmetry of the molecule, the presence of terminal substituents, and the molecular size) and define on that basis the molecular features required to maximize the charge carrier mobility within the channels. In particular, we demonstrate that a strong localization of the molecular orbitals in push,pull compounds is generally detrimental to the charge transport properties. [source]

Experimental and Theoretical Characterization of a Triplet Boron Carbonyl Compound: BBCO

CHEMPHYSCHEM, Issue 7 2003
Mingfei Zhou Prof.
Unusually generous donation: Matrix isolation infrared spectroscopy and quantum chemical calculations characterize the new boron carbonyl compound BBCO (see graphic), which has a linear triplet ground state (3,,). The binding energy of CO and BB is quite large, due to the back bonding usually associated with transition metal carbonyl complexes. [source]

Theoretical characterizations of HAsXH (X = N, P, As, Sb, and Bi) isomers in the singlet and triplet states

Chin-Hung Lai
Abstract The lowest singlet and triplet potential energy surfaces for all group 15 HAsXH (X = N, P, As, Sb, and Bi) systems have been explored through ab initio calculations. The geometries of the various isomers were determined at the QCISD/LANL2DZdp level and confirmed to be minima by vibrational analysis. In the case of nitrogen, the global minimum is found to be a triplet H2NAs structure. For the phosphorus case, singlet trans -HAsPH is found to be global minima surrounded by large activation barriers, so that it should be observable. For arsenic, theoretical investigations demonstrate that the stability of HAsAsH isomers decreases in the order singlet trans -HAsAsH > triplet H2AsAs > singlet cis -HAsAsH > triplet HAsAsH > singlet H2AsAs. For antimony and bismuth, the theoretical findings suggest that the stability of HAsXH (X = Sb and Bi) systems decreases in the order triplet H2AsX , singlet trans -HAsXH > singlet cis -HAsXH > triplet HAsXH > triplet H2XAs > singlet H2AsX > singlet H2XAs. Our model calculations indicate that the relativistic effect on heavier group 15 elements should play an important role in determining the geometries as well as the stability of HAsXH molecules. The results obtained are in good agreement with the available experimental data and allow a number of predictions to be made. 2008 Wiley Periodicals, Inc. J Comput Chem, 2008 [source]

Molecular relaxation and metalloenzyme active site modeling

James W. Whittaker
Abstract Metalloenzymes represent a broad class of important biomolecules containing an essential metal ion cofactor in their catalytic active sites, forming biologic metal complexes that perform a wide range of important functions: activation of small molecules (O2, N2, H2, CO), atom transfer chemistry, and the control of oxidation equivalents. The structures of many metalloenzyme active sites have been defined by X-ray crystallography, revealing transition metal ions in unique low-symmetry environments. These bioinorganic complexes present significant challenges for computational studies aimed at going beyond crystal structures to develop a detailed understanding of the catalytic mechanisms. Considerable progress has been made in the theoretical characterization of these sites in recent years, supported by the availability of efficient computational tools, in particular density functional methods. However, the ultimate success of a theoretical model depends on a number of factors independent of the specific computational method used, including the quality of the initial structural data, the identification of important environmental perturbations and constraints, and experimental validation of theoretical predictions. We explore these issues in detail and illustrate the effects of molecular relaxation in calculations of two metalloenzymes, manganese superoxide dismutase and galactose oxidase. 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 [source]