Search results for "ELECTRONIC STRUCTURE"
showing 10 items of 722 documents
Internally Contracted Multireference Coupled Cluster Calculations with a Spin-Free Dirac-Coulomb Hamiltonian: Application to the Monoxides of Titaniu…
2017
We combine internally contracted multireference coupled cluster theory with a four-component treatment of scalar-relativistic effects based on the spin-free Dirac–Coulomb Hamiltonian. This strategy allows for a rigorous treatment of static and dynamic correlation as well as scalar-relativistic effects, which makes it viable to describe molecules containing heavy transition elements. The use of a spin-free formalism limits the impact of the four-component treatment on the computational cost to the non-rate-determining steps of the calculations. We apply the newly developed method to the lowest singlet and triplet states of the monoxides of titanium, zirconium, and hafnium and show how the in…
Theoretical Simulations on Electric Properties of CNT-Me and GNR-Me Interconnects Using Effective Media Approach
2011
Abstract To overcome disadvantages of nowadays microtechnology, a further miniaturization of electronic devices, high integration level as well as increase of both operation frequencies and power density is required, including the use of adequate materials and innovative chip interconnects. Due to their unique physical properties, especially due to a ballistic (without losses) mechanism of conductivity, carbon nanotubes (CNTs) and graphene nanoribbons (GNRs) attract a permanently growing technological interest, for example, as promising candidates for nanointerconnects in a high-speed electronics.
A critical size for emergence of nonbulk electronic and geometric structures in dodecanethiolate-protected Au clusters.
2014
We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to ∼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(∼226)(SC12)(∼76), Au(∼253)(SC12)(∼90), Au(∼356)(SC12)(∼112), and Au(∼520)(SC12)(∼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like elec…
An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand
2018
[W(N2O2)(HN2O2)] (H4N2O2 = N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)3] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate amidophenoxide ligand. The formal oxidation s…
Computational investigations of 18-electron triatomic sulfur–nitrogen anions
2018
MRCI-SD/def2-QZVP and PBE0/def2-QZVP calculations have been employed for the analysis of geometries, stabilities, and bonding of isomers of the 18-electron anions N2S2−, NS2−, and NSO−. Isomers of the isoelectronic neutral molecules SO2, S2O, S3, and O3 are included for comparison. The sulfur-centered acyclic NSN2−, NSS−, and NSO− anions are the most stable isomers of their respective molecular compositions. However, the nitrogen-centered isomers SNS− and SNO− lie close enough in energy to their more stable counterparts to allow their occurrence. The experimental structural information, where available, is in good agreement with the optimized bond parameters. The bonding in all investigate…
Do Extremely Bent Allenes Exist?
2009
Bent allenes: Theoretical calculations show that extremely bent allenes, cyclic or acyclic, adopt a ground state that only bears a formal relationship to classical allenes. Consequently, five-membered ring allenes favor a carbene-like electronic structure and formally contain a trivalent carbon(II) center. peerReviewed
On Transition Structures for Hydride Transfer Step: A Theoretical Study of the Reaction Catalyzed by Dihydrofolate Reductase Enzyme
1996
Abstract A theoretical study is presented of the catalytic mechanism of dihydrofolate reductase (DHFR) enzyme based upon the characterization of the transition structure (TS) for the hydride transfer step. Analytical gradients at AM1 and PM3 semiempirical levels have been used to characterize the saddle point of index one (SPi-1) on global energy hypersurface for the hydride transfer in the active site of DHFR enzyme. The geometry, stereochemistry, electronic structure, and transition vector (TV) components associated to SPi-1 are qualitatively computational level independent. The TV amplitudes show primary and secondary isotope effects to be strongly coupled. The geometrical arrangement of…
Quantum wells within quantum dots, a CdS/HgS nanoheterostructure with global and local confinement
1998
Semiconductor nanocrystals prepared by methods of wet chemistry are similar to MBE grown quantum dots where the mobility of the charge carriers is reduced to zero dimensionality. In this paper we summarize the physics of a unique system in which the charge carriers are locally confined within a heterogeneous quantum dot. With high resolution electron microscopy we will show that epitaxial growth ot atomic layer precision is possible by methods of solution chemistry leading to CdS quantum dots with embedded HgS quantum wells (QDQWs). The photophysics of this system is investigated by time-correlated single photon counting, transient differential absorption and fluorescence line narrowing spe…
Geometric and electronic structure of dithiapyranylidine: evolution upon oxidation
1993
Abstract We present a theoretical investigation of the modifications that successive oxidation induces on the geometric and electronic structures of the π-electron donor dithiapyranylidene. The lengthening of the double bonds and the shortening of the single bonds calculated as the molecular charge increases indicate a gain of aromaticity with oxidation. Both the geometricand the electronic structure of dithiapyranylidene show a clear evolution towards those of biphenyl as oxidation takes place.
Experimental and theoretical studies on the electronic spectra of indole-3-acetic acid and its anionic and protonated species
1991
Abstract The geometrical and electronic structure of indole-3-acetic acid (IAH) have been investigated using the MINDO/3 molecular orbital method, the geometries being optimized by Rinaldi's method. The UV spectrum of IAH has been recorded in different solvents. The corresponding spectra of IAH + 2 and IA − were also respectively obtained, from IAH in different H 2 SO 4 /water mixtures and NaOH solutions. The agreement of experimental spectra with the ones theoretically calculated by the CNDO/M-Cl method after optimization of the κ parameter, is discussed. The p K a values of IAH have also been determined from the IAH + 2 spectra and are compared with literature data.