Search results for "localize"
showing 10 items of 300 documents
High pressure theoretical and experimental analysis of the bandgap of BaMoO4, PbMoO4, and CdMoO4
2019
We have investigated the origin of the bandgap of BaMoO4, PbMoO4, and CdMoO4 crystals on the basis of optical absorption spectroscopy experiments and ab initio electronic band structure, density of states, and electronic localization function calculations under high pressure. Our study provides an accurate determination of the bandgaps Eg and their pressure derivatives d E g / dP for BaMoO4 (4.43 eV, −4.4 meV/GPa), PbMoO4 (3.45 eV, −53.8 meV/GPa), and CdMoO4 (3.71 eV, −3.3 meV/GPa). The absorption edges were fitted with the Urbach exponential model which we demonstrate to be the most appropriate for thick crystals with direct bandgaps. So far, the narrowing of the bandgap of distinct PbMoO4…
The substituent effect of π-electron delocalization in N-methylamino-nitropyridine derivatives: crystal structure and DFT calculations
2020
AbstractThe crystal and molecular structures of 3-(N-methylamino)-2-nitropyridine, 5-(N-methylamino)-2-nitropyridine and 2-(N-methylamino)-5-nitropyridine have been characterized by X-ray diffraction. To perform conformational analysis, the geometries of the compounds as well as their conformers and rotamers were optimized at the B3LYP/6-311++G(3df,3pd) level. The resulting data were used to analyze the π-electron delocalization effect in relation to the methylamino group rotation in ortho-, meta- and para-substitution positions. Quantitative aromaticity indices were calculated based on which we estimated the electronic structures of the analyzed compounds. The substituent effect of the met…
Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad
2018
Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…
Synthesis, molecular structures and EPR spectra of the paramagnetic cuboidal clusters with Mo3S4Ga cores
2017
Electron precise [Mo3(l3-S)(l-S)3(diphos)3Br3]Br (diphos = dppe, dmpe) incomplete cuboidal clusters with six cluster skeletal electrons (CSE) were converted into paramagnetic cuboidal [Mo3(GaBr)(l3-S)4- (diphos)3Br3] clusters by treatment with elemental Ga. The new heterobimetallic complexes with nine CSE possess a doublet ground state with the unpaired electron density delocalized over the three molybdenum atoms.
Vibronic Model for Intercommunication of Localized Spins via Itinerant Electron
2019
In this article, we propose a vibronic pseudo Jahn–Teller model for partially delocalized mixed-valence molecules aimed to describe the magnetic coupling between the localized spins mediated by the delocalized electron. The simplest partially delocalized system that retains the main studied features is assumed to consist of a one-electron mixed-valence dimer, which is connected to the two terminal magnetic ions. The model involves the following key interactions: electron transfer in the spin-delocalized subsystem of a mixed-valence molecule, which is mimicked by a dimeric unit, coupling of the itinerant electrons with the molecular vibrations, and isotropic magnetic exchange between the loc…
Electron Spin Resonance study of charge trapping in α-ZnMoO4 single crystal scintillator
2015
The origin and properties of electron and hole traps simultaneously appearing in a-ZnMoO4 scintillator after X-ray irradiation at low temperatures (T < 35 K) were studied by Electron Spin Resonance (ESR). ESR spectrum of the electron type trap shows pronounced superhyperfine structure due to the interaction of electron spin with nuclear magnetic moments of 95,97Mo and 67Zn lattice nuclei. Considering the nearly tetragonal symmetry of the center this allows us to identify the electron trap as an electron self-trapped at the (Mo(1)O4) 2 complex. Nearly 60% reduction of the spin–orbit coupling at the Mo(1) ion is caused by the overlap of the Mo and ligand oxygen orbitals indicating an essentia…
Localized Interleukin-12 for Cancer Immunotherapy
2020
Interleukin-12 (IL-12) is a potent, pro-inflammatory type 1 cytokine that has long been studied as a potential immunotherapy for cancer. Unfortunately, IL-12's remarkable antitumor efficacy in preclinical models has yet to be replicated in humans. Early clinical trials in the mid-1990's showed that systemic delivery of IL-12 incurred dose-limiting toxicities. Nevertheless, IL-12's pleiotropic activity, i.e., its ability to engage multiple effector mechanisms and reverse tumor-induced immunosuppression, continues to entice cancer researchers. The development of strategies which maximize IL-12 delivery to the tumor microenvironment while minimizing systemic exposure are of increasing interest…
Efficient Linear-Scaling Density Functional Theory for Molecular Systems
2013
Despite recent progress in linear scaling (LS) density function theory (DFT), the computational cost of the existing LS methods remains too high for a widespread adoption at present. In this work, we exploit nonorthogonal localized molecular orbitals to develop a series of LS methods for molecular systems with a low computational overhead. High efficiency of the proposed methods is achieved with a new robust two-stage variational procedure or by replacing the optimization altogether with an accurate nonself-consistent approach. We demonstrate that, even for challenging condensed-phase systems, the implemented LS methods are capable of extending the range of accurate DFT simulations to molec…
Theoretical study of the NH tautomerism in free base porphyrin
1997
Abstract The NH tautomerism of free base porphyrin is investigated at the semiempirical spin-unrestricted AM1 (UAM1) and ab initio RHF/3-21G levels. The UAM1 method provides delocalized geometries for all stationary structures without imposing any symmetry constraint. RHF/3-21G geometry optimizations have to be performed under symmetry restrictions to ensure that realistic delocalized structures are obtained. Both the semiempirical and the ab initio calculations predict that the interconversion between trans tautomers proceeds in an asynchronous two-step process via intermediate cis tautomers. The cis tautomers are characterized as minima in the potential energy surface and are 8–10 kcal m…
Semiclassical approximation in the magnetic problem of exchange-coupled mixed valence clusters
1994
Abstract The frameworks of the applicability of the semiclassical adiabatic approach suggested by Borras-Almenar, Coronado and Tsukerblat to the magnetic problem of mixed valence clusters are considered in a model taking into account magnetic exchange, double exchange and vibronic interaction. The results for the quantum-mechanical and semicalssical calculation of the temperature-variable magnetic moments are compared with those within the scope of the semiclassical approximation for the dimeric d 1 —d 2 clusters and trimeric d 1 —d 1 —d 2 systems with partial delocalization over a pair of ions. The semiclassical approach describes with high accuracy the temperature dependencies of the magn…