Search results for " orbita"
showing 10 items of 447 documents
The first unpaired electron placed inside a C3-symmetry P-chirogenic cluster
2010
The Pd(3)(dppm*)(3)(CO)(n+) enantiomers (n = 2 (2), 1 (3)) were prepared either from (R,R)- or (S,S)-P-chirogenic bis(phenyl-m-xylylphosphino)methane (dppm*; 1) and Pd(OAc)(2) in the presence of CF(3)CO(2)H, CO and water (n = 2), and then by reductive electrolysis (n = 1). The stable enantiomeric [Pd(3)((S,S)-dppm*)(3)(CO)](+)˙ (3), is the first C(3)-symmetry radical-cation M-M bonded cluster, therefore the odd electron is delocalized onto the Pd(3) frame within this symmetry. The novel chiral species have been characterized by circular dichroism (CD) of both enantiomers of the Pd(3)(dppm*)(3)(CO)(2+) clusters (2) and by EPR spectroscopy for the Pd(3)((S,S)-dppm*)(3)(CO)(+)˙ paramagnetic co…
Density functional theory fragment descriptors to quantify the reactivity of a molecular family: Application to amino acids
2007
By using the exact density functional theory, one demonstrates that the value of the local electronic softness of a molecular fragment is directly related to the polarization charge (Coulomb hole) induced by a test electron removed (or added) from (at) the fragment. Our finding generalizes to a chemical group a formal relation between these molecular descriptors recently obtained for an atom in a molecule using an approximate atomistic model [P. Senet and M. Yang, J. Chem. Sci. 117, 411 (2005)]. In addition, a practical ab initio computational scheme of the Coulomb hole and related local descriptors of reactivity of a molecular family having in common a similar fragment is presented. As a b…
Toward an Understanding of the Catalytic Role of Hydrogen-Bond Donor Solvents in the Hetero-Diels−Alder Reaction between Acetone and Butadiene Deriva…
2006
A detailed theoretical investigation of the catalytic role of hydrogen-bond- (HB-) donor molecules (water, methanol, chloroform, dichloromethane, and chloromethane) in the hetero-Diels-Alder reaction between acetone and N,N-dimethyl-1-amino-3-methoxy-1,3-butadiene is presented. This work extends a previous study (Domingo, L. R.; Andres, J. J. Org. Chem. 2003, 68, 8662) in which the importance of weak HB-donor solvents to catalyze more effectively than solvents with a higher dielectric constant but no HB-donor capability was analyzed. Now, based on density functional theory (DFT) at B3LYP/6-31+G(d) level calculations, different techniques for analyzing the nature of HB interaction, namely, n…
Photoswitchable Micro-Supercapacitor Based on a Diarylethene-Graphene Composite Film
2017
Stimuli-responsive micro-supercapacitors (MSCs) controlled by external stimuli can enable a wide range of applications for future on-chip energy storage. Here, we report on a photoswitchable MSC based on a diarylethene-graphene composite film. The microdevice delivers an outstanding and reversible capacitance modulation of up to 20%, demonstrating a prototype photoswitchable MSC. Terahertz spectroscopy indicates that the photoswitching of the capacitance is enabled by the reversible tuning of interfacial charge injection into diarylethene molecular orbitals, as a consequence of charge transfer at the diarylethene-graphene interface upon light modulation.
Titania nanotubes modeled from 3- and 6-layered (101) anatase sheets: Line group symmetry and comparative ab initio LCAO calculations
2010
Abstract The formalism of line groups for one-periodic (1D) nanostructures with rotohelical symmetry has been applied for construction of TiO 2 nanotubes (NTs). They are formed by rolling up the stoichiometric two-periodic (2D) sheets cut from the energetically stable (1 0 1) anatase surface, which contains either six (O–Ti–O_O–Ti–O) or three (O–Ti–O) layers. After optimization of geometry the former keeps the centered rectangular symmetry of initial slab while the latter is spontaneously reconstructed to the hexagonal fluorite-type (1 1 1) sheet. We have considered the four sets of TiO 2 NTs with optimized 6- and 3-layered structures, which possess the two pairs of either anatase (− n , n …
Ab initio simulations on N and S co-doped titania nanotubes for photocatalytic applications
2015
In this paper we present the results of quantum chemical modeling for energetically stable anatase (001) TiO2 nanotubes, undoped, doped, and codoped with N and S atoms. We calculate the electronic structure of one-dimensional (1D) nanotubes and zero-dimensional (0D) atomic fragments cut out from these nanotubes, employing hybrid density functional theory with a partial incorporation of an exact, nonlocal Hartree–Fock exchange within the formalism of the linear combination of atomic orbitals, as implemented in both CRYSTAL and NWChem total energy codes. Structural optimization of 1D nanotubes has been performed using CRYSTAL09 code, while the cut-out 0D fragments have been modelled using the…
First principles modeling of 3d-metal doped three-layer fluorite-structured TiO2 (4,4) nanotube to be used for photocatalytic hydrogen production
2017
This study has been supported by the EC ERA.Net RUS Plus project No. 237 WATERSPLIT, Russian Basic Research Foundation No. 16-53-76019, and additionally by the IMIS2 Program (Latvia). The authors are also indebted to R. A. Evarestov and O. Lisovski for stimulating discussions as well as to A. Chesnokov for technical assistance.
Symmetry and Models of Double-Wall BN and TiO2 Nanotubes with Hexagonal Morphology
2011
The line symmetry groups for one-periodic (1D) nanostructures with rotohelical symmetry have been applied for symmetry analysis of double-wall boron nitride and titania nano- tubes (DW BN and TiO2 NTs) formed by rolling up the stoichiometric two-periodic (2D) slabs of hexagonal structure with the same or opposite orientation of translation and chiral vectors. We have considered the two sets of commensurate DW BN and TiO2 NTs with either armchair- or zigzag-type chiralities, i.e., (n1,n1)@(n2,n2 )o r (n1,0)@(n2,0), respectively. To establish theequilibriuminterwalldistancescorrespondingtotheminimaof energy, we have varied chiral indices n1 and n2 of the constituent single-wall (SW) nanotubes…
Strongly Red-Emissive Molecular Ruby [Cr(bpmp)2]3+ Surpasses [Ru(bpy)3]2+
2021
Gaining chemical control over the thermodynamics and kinetics of photoexcited states is paramount to an efficient and sustainable utilization of photoactive transition metal complexes in a plethora of technologies. In contrast to energies of charge transfer states described by spatially separated orbitals, the energies of spin-flip states cannot straightforwardly be predicted as Pauli repulsion and the nephelauxetic effect play key roles. Guided by multireference quantum chemical calculations, we report a novel highly luminescent spin-flip emitter with a quantum chemically predicted blue-shifted luminescence. The spin-flip emission band of the chromium complex [Cr(bpmp)2]3+ (bpmp = 2,6-bis(…
640-Slice CT Measurement of Superior Orbital Fissure as Gateway for Light into the Brain: Statistical Evaluation of Area and Distance.
2016
Objective Our aim was to provide normative data concerning superior orbital fissure area (SOFA), ocular skin and the substantia nigra (D-SS) and orbital fissure and the substantia nigra (D-SOF-S) distances by CT scan in adult Caucasian population. Methods The area of the superior orbital fissure (SOF), the distance between the ocular skin and the substantia nigra and the distance between the superior orbital fissure and the substantia nigra using CT and 3D-CT images. Results Normative data stratified for age and gender were obtained. The data here reported show that some degree of variability in SOFA, D-SS and D-SOF-S measurements can be observed healthy Caucasian subjects. Gender stratifie…