Electron localization function for transition-metal compounds

 The analysis of the electron localization function of molecules and solids needs to involve the atomic core regions as well to reveal a more detailed insight into the bonding situation. Received: 20 February 2002 /Accepted: 14 June 2002 /Published online: 19 August 2002     

Electron localization function as information measure

The conditional two-electron probability function, which defines the electron localization function (ELF) of Becke and Edgecombe in the Kohn-Sham theory, is interpreted as the nonadditive (interorbital) Fisher information contained in the electron distribution. The probability normalization considerations suggest a use of the related information measure defined in terms of the unity-normalized probability distributions (shape factors of the electron densities), as the key ingredient of the modified information-theoretic ELF. This modified Fisher information density is validated by a comparison with the original two-electron probability function. Illustrative applications to typical molecular systems demonstrate the adequacy of the modified information-theoretic ELF in extracting the key features of the electron distributions in molecules. The overall Fisher information itself and the associated information-distance quantities are also proposed as complementary localization functions.     

Electron localization function from density components

This work addresses the decomposition of the Electron Localization Function (ELF) into partial density contributions using an appealing split of kinetic energy densities. Regarding the degree of the electron localization, the relationship between ELF and its usual spin‐polarized formula is discussed. A new polarized ELF formula, built from any subsystems of the density, and a localization function, quantifying the measure of electron localization for only a subpart of the total system are introduced. The methodology appears tailored to describe the electron localization in bonding patterns of subsystems, such as the local nucleophilic character. Beyond these striking examples, this work opens up opportunities to describe any electronic properties that depend only on subparts of the density in atoms, molecules, or solids. © 2016 Wiley Periodicals, Inc.     

Electron localization function at the correlated level

The electron localization function (ELF) has been proven so far a valuable tool to determine the location of electron pairs. Because of that, the ELF has been widely used to understand the nature of the chemical bonding and to discuss the mechanism of chemical reactions. Up to now, most applications of the ELF have been performed with monodeterminantal methods and only few attempts to calculate this function for correlated wave functions have been carried out. Here, a formulation of ELF valid for mono- and multiconfigurational wave functions is given and compared with previous recently reported approaches. The method described does not require the use of the homogeneous electron gas to define the ELF, at variance with the ELF definition given by Becke. The effect of the electron correlation in the ELF, introduced by means of configuration interaction with singles and doubles calculations, is discussed in the light of the results derived from a set of atomic and molecular systems.     

Electron interactions in crystalline dibenzotetraazaannulene

The characteristics of intra- and intermolecular electronic processes in crystalline dibenzotetraazaannulene were established based on an analysis of the electronic absorption spectra of thin films. It was shown that the specific spectral characteristics of this substance are due to its stack structure in the solid state.L V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 252039 Kiev, Prosp. Nauki, 31. Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 32, No. 1, pp. 20–23, January–February, 1996. Original article submitted May 19, 1995.     

Liquid crystalline materials for light-emitting diodes

Liquid crystalline materials display unique properties which can be exploited in organic light-emitting diodes. Characteristic features of liquid crystals are the anisotropy of electronic properties, a strong coupling to external fields as well as a tendency to form spontaneously homogeneous monodomain films. It is found that liquid crystalline materials can be used in light-emitting diodes to control the state of polarization of the emitted light, the magnitude of the onset field for emission as well as the quantum efficiency. Both low molar mass and polymeric liquid crystals have been introduced with great success in single as well as in multilayer devices. © 1998 John Wiley & Sons, Ltd.     

Electron localization and delocalization indices for solids

The electron localization and delocalization indices obtained by the integration of exchange‐correlation part of pair density over chemically meaningful regions of space, e.g., QTAIM atoms are valuable tools for the bonding analysis in molecular systems. However, among periodic systems only few simplest models were analyzed with this approach until now. This contribution reports implementation and evaluation of the localization and delocalization indices on the basis of solid state DFT calculations. A comparison with the results of simple analytical model of Ponec was made. In addition, a small set of compounds with ionic (NaCl), covalent (diamond, graphite), and metallic (Na, Cu) bonding interactions was characterized using this method. Typical features of different types of bonding were discussed using the delocalization indices. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Electron pair localization function: a practical tool to visualize electron localization in molecules from quantum Monte Carlo data

In this work we introduce an electron localization function describing the pairing of electrons in a molecular system. This function, called "electron pair localization function," is constructed to be particularly simple to evaluate within a quantum Monte Carlo framework. Two major advantages of this function are the following: (i) the simplicity and generality of its definition; and (ii) the possibility of calculating it with quantum Monte Carlo at various levels of accuracy (Hartree-Fock, multiconfigurational wave functions, valence bond, density functional theory, variational Monte Carlo with explicitly correlated trial wave functions, fixed-node diffusion Monte Carlo, etc). A number of applications of the electron pair localization function to simple atomic and molecular systems are presented and systematic comparisons with the more standard electron localization function of Becke and Edgecombe are done. Results illustrate that the electron pair localization function is a simple and practical tool for visualizing electronic localization in molecular systems.     

Comparison of the electron localization function and deformation electron density maps for selected earth materials

The electron localization function (ELF) and experimental and theoretical deformation electron density maps are compared for several earth materials and one representative molecule. The number and arrangement of the localized one-electron probability density domains generated in a mapping of the ELF correspond to the number and arrangement of the localized electron density domains generated in a mapping of the deformation electron density distribution, a correspondence that suggests that the two fields are homeomorphically related. As a homeomorphic relationship has been established previously between the Laplacian of the electron density distribution and the ELF, the relationship suggests that the deformation electron density distribution is also homeomorphically related to the Laplacian of the distribution.     

Electron localization function study on intramolecular electron transfer in the QTTFQ and DBTTFI radical anions

The unsymmetrical distribution of the unpaired electron in the ground state of the DBTTFI(?-) radical anion (bi(6-n-butyl-5,7-dioxo-6,7-dihydro-5H-[1,3]dithiolo[4,5-f]isoindole-2-ylidene) is theoretically predicted using the M06-2X/6-31+G(d,p) level of calculations. The results are additionally confirmed by single point calculations at B3LYP/aug-cc-pVTZ, LC-ωPBE/aug-cc-pVTZ, and M06-2X/aug-cc-pVTZ levels. DBTTFI, containing the TTF (tetrathiafulvalene) fragment, may be used in the construction of organic microelectronic devices, similarly to the radical anion of QTTFQ. The unsymmetrical distribution of spin density in (QTTFQ)(?-) has been confirmed using M06-2X/aug-cc-pVTZ calculations, with subsequent study using topological analysis of electron localization function (ELF). The reorganization of the chemical bonds during intramolecular electron transfer in (QTTFQ)(?-) and (DBTTFI)(?-) has been analyzed using bonding evolution theory (BET). The reaction path has been simulated by the IRC procedure, and the evolution of valence basins has been described using catastrophe theory. The simple mechanisms: (QTTFQ)(?-): η-1-3-CC(+)-0: (-?)(QTTFQ) and (DBTTFI)(?-): η-1-3-[F](4)[F(+)](4)-0: (-?)(DBTTFI), each consisting of three steps, have been observed. Two cusp or 4-fold catastrophes occur immediately after the TS. Our study shows that potential future microelectronic devices, constructed on the basis of the (QTTFQ)(?-) and (DBTTFI)(?-) systems, should exploit the properties of the C═C bond.     

A single-tilt TEM stereomicroscopy technique for crystalline materials.

A new single-tilt technique for performing TEM stereomicroscopy of strain fields in crystalline materials has been developed. The technique is a weak beam technique that involves changing the value of g and/or s g while tilting across a set of Kikuchi bands. The primary benefit of the technique is it can be used with single-tilt TEM specimen holders including many specialty holders such as in situ straining, heating, and cooling holders. Standard stereo-TEM techniques are almost always limited to holders allowing two degrees of rotational freedom (i.e., double-tilt or tilt/rotation holders). An additional benefit of the new technique is that it eliminates the need to focus with the specimen height control. These advantages make it useful for stereo viewing or for quantitative stereomicroscopy provided necessary consideration is given to errors that may result from the technique.     

Electron localization and delocalization in open-shell molecules

Localization and delocalization indices derived in the framework of the quantum Atoms in Molecules theory have recently been used to analyze the electron-pair structure of closed-shell molecules. Here we report calculations of localization and delocalization indices for open-shell molecules at the Hartree-Fock (HF) level. Several simple doublet and triplet radical molecules are studied. In general, interatomic delocalization between bonded atoms is heavily dependent on the order and polarity of the bond. Unpaired electrons also have a significant effect on the interatomic delocalization indices. Indeed, for many radicals, the analysis of the spin components reveals that the interatomic delocalization is very different for alpha and beta spin electrons in many cases. In general, at the HF level, the results can be rationalized in terms of orbital contributions. However, the definition of localization and delocalization indices is completely general, and they could be calculated at any level of theory, provided that the one- and two-electron densities are available.     

Electron localization in a finite one-dimensional chain

The localization characteristics of the electronic wave functions in a finite one-dimensional chain with the diagonal or the off-diagonal disorder of the potentials have been studied. It has been shown that the eigenfuction at the frontier level is relatively “strong” against the temptation to localize caused by the existence of the random potentials. It has also been pointed out that the spatial behavior of the total density reflects that of the diagonal random potentials, but that under the off-diagonal random potentials the total density is spatially uniform (completely extended).     

Electron solvation in crystalline ice on a subnanosecond timescale

The optical absorption resulting from pulse radiolysis of ice has been studied with subnanosecond resolution. The half-time for electron solvation is ≈ 400 ps at ?5°C. A species with a spectrum similar to that of the “solvated” electron is formed within the 30 ps time resolution of the measurements and decays over several hundred picoseconds.     

光致变色液晶材料研究进展

本文介绍了液晶相态和光致变色的基本原理,液晶材料在光学领域中的应用,光致变色化合物的光异构化反应对液晶光学性质的影响,以及光致变色液晶材料制备的进展。参考文献53篇。     

Structure-fluorescence relationships in pyrrole appended o-carborane crystalline materials

Based on three rationally designed pyrrole-appended o-carborane derivatives, we present that fluorescence properties of crystalline materials are highly dependent on intermolecular interaction and steric hinderance. Though the three molecules are similar in structure, single crystals of the three compounds showed obvious difference in molecular stacking and fluorescence behavior. Systematic studies indicate that fluorescence quantum yields, thermo-response as well as mechano-response are highly ...     

Modelling of shear flow in liquid crystalline materials

The flow behaviour of liquid crystalline polymers (LCPs) is quite complex and these materials exhibit varied and complicated textural patterns when subject to a flow field. The complexity arises from two general factors, the first that they are long chained and thus have long relaxation times, and second that they are liquid crystalline, and thus there is co-operative motion of the molecules. In both thermotropic and lyotropic LCPs subject to low shear flows, it is known that defects and disclinations influence the microstructure and rheology, but it is not clear by what mechanisms these distortions shrink or multiply during flow. In this work, a model is developed to examine the behaviour of defects in shear flows. The simulations based on the model show a spectrum of microstrucural development as a function of applied shear rate: reorientation of domains of different alignment associated with disclinations at low shear strains; the multiplication of wall type defects and the orientation of these normal to the shear gradient axis at intermediate shear rates, and the tendency towards disclination annihilation; the generation of a flow-aligned monodomain at higher shear rates.     

Modelling of shear flow in liquid crystalline materials

The flow behaviour of liquid crystalline polymers (LCPs) is quite complex and these materials exhibit varied and complicated textural patterns when subject to a flow field. The complexity arises from two general factors, the first that they are long chained and thus have long relaxation times, and second that they are liquid crystalline, and thus there is co-operative motion of the molecules. In both thermotropic and lyotropic LCPs subject to low shear flows, it is known that defects and disclinations influence the microstructure and rheology, but it is not clear by what mechanisms these distortions shrink or multiply during flow. In this work, a model is developed to examine the behaviour of defects in shear flows. The simulations based on the model show a spectrum of microstrucural development as a function of applied shear rate: reorientation of domains of different alignment associated with disclinations at low shear strains; the multiplication of wall type defects and the orientation of these normal to the shear gradient axis at intermediate shear rates, and the tendency towards disclination annihilation; the generation of a flow-aligned monodomain at higher shear rates.