Topological methods of quantum chemistry for a study of chemical reactivity

1980 ◽  
Vol 45 (9) ◽  
pp. 2452-2462 ◽  
Author(s):  
Jiří Pancíř
Keyword(s):  
Electronic Structures ◽  
Chemical Reactivity ◽  
Average Error ◽  
Medium Size ◽  
Electron Pairs ◽  
Hartree Fock ◽  
Structural Formulas ◽  
Quantum Chemical Model ◽  
Core Electrons ◽  
The One

In this paper all approximations are discussed which lead to a quantum chemical model which is adequate for structural formulas known in classical organic chemistry. Neglect of the energy differences caused by changes of valence and dihedral angles, i.e. neglect of all nonbonding interactions, leads to the separation of the Hartree-Fock matrix in blocks of core electrons, nonbonding electron pairs, two center blocks of σ-bonds and delocalized π-electronic structures. Such a procedure can be formulated at all levels of sophistication - from the one electron approximation to the MC-SCF method. Even on the one electron level, the average error in heats of atomization (35.9 kJ/mol) is lower than that of the more complicated geometrical methods MINDO/3 (52.1 kJ/mol) and MNDO (39.6 kJ/mol). The procedure suggested is about two orders of magnitude more efficient than geometrical ones of the same level and can be, therefore, used for a study of reaction mechanisms of medium size systems (30-50 atoms) without large expense.

Spatially Resolved Photoelectron Spectroscopy: Recent Progress and Future Plans

1990 ◽  
Vol 48 (2) ◽  
pp. 388-389
Author(s):  
A. M. Bradshaw
Keyword(s):  
Photoelectron Spectroscopy ◽  
Chemical Reactivity ◽  
Target Material ◽  
Orbital Energy ◽  
Light Sources ◽  
Analytical Technique ◽  
Hartree Fock ◽  
Spatially Resolved ◽  
Koopmans Theorem ◽  
Surface Analytical Technique

X-ray photoelectron spectroscopy (XPS or ESCA) was not developed by Siegbahn and co-workers as a surface analytical technique, but rather as a general probe of electronic structure and chemical reactivity. The method is based on the phenomenon of photoionisation: The absorption of monochromatic radiation in the target material (free atoms, molecules, solids or liquids) causes electrons to be injected into the vacuum continuum. Pseudo-monochromatic laboratory light sources (e.g. AlKα) have mostly been used hitherto for this excitation; in recent years synchrotron radiation has become increasingly important. A kinetic energy analysis of the so-called photoelectrons gives rise to a spectrum which consists of a series of lines corresponding to each discrete core and valence level of the system. The measured binding energy, EB, given by EB = hv−EK, where EK is the kineticenergy relative to the vacuum level, may be equated with the orbital energy derived from a Hartree-Fock SCF calculation of the system under consideration (Koopmans theorem).

History and Cross-Disciplinary Perspective of Compositional Imaging and Mapping With Nexafs Microscopy

1998 ◽  
Vol 4 (S2) ◽  
pp. 154-155
Author(s):  
H. Ade
Keyword(s):  
Electronic Structures ◽  
Chemical Shifts ◽  
Electronic States ◽  
Inorganic Materials ◽  
Chemical Bonds ◽  
Fundamental Physics ◽  
X Ray ◽  
Disciplinary Perspective ◽  
Core Electrons ◽  
X Ray Absorption

In Near Edge X-ray Absorption Fine Structure (NEXAFS) microscopy, excitations of core electrons into unoccupied molecular orbitals or electronic states provide sensitivity to a wide variety of chemical functionalities in molecules and solids. This sensitivity complements infrared (IR) spectroscopy, although the NEXAFS spectra are not quite as specific and “rich” as IR spectra. The sensitivity of NEXAFS to distinguish chemical bonds and electronic structures covers a wide variety of samples: from metals to inorganics and organics. (There is a tendency in the community to use the term NEXAFS for soft x-ray spectroscopy of organic materials, while for inorganic materials or at higher energies X-ray Absorption Near Edge Spectroscopy (XANES) is utilized, even though the fundamental physics is the same.) The sensitivity of NEXAFS is particularly high to distinguish saturated from unsaturated bonds. NEXAFS can also detect conjugation in a molecule, as well as chemical shifts due to heteroatoms.

scholarly journals EXPANSION FORMULAE FOR ONE- AND TWO-CENTER CHARGE DENSITIES OVER COMPLETE ORTHONORMAL SETS OF EXPONENTIAL TYPE ORBITALS AND THEIR USE IN EVALUATION OF MULTICENTER–MULTIELECTRON INTEGRALS

2009 ◽  
Vol 08 (04) ◽  
pp. 597-602 ◽  
Author(s):  
I. I. GUSEINOV
Keyword(s):  
Exponential Type ◽  
Overlap Integrals ◽  
Charge Densities ◽  
Hartree Fock ◽  
Expansion Formulae ◽  
Multicenter Multielectron Integrals ◽  
Explicitly Correlated ◽  
Explicitly Correlated Methods ◽  
Exponential Type Orbitals ◽  
The One

The series expansion formulae are established for the one- and two-center charge densities over complete orthonormal sets of Ψα-exponential type orbitals (Ψα-ETO α = 1,0,-1,-2,…) introduced by the author. Three-center overlap integrals of Ψα appearing in these relations are expressed through the two-center overlap integrals between Ψα-orbitals. The general formulae obtained for the charge densities are utilized for the evaluation of arbitrary multicenter–multielectron integrals occurring when the complete orthonormal sets of Ψα-ETO are used as basis functions in the Hartree–Fock–Roothaan and explicitly correlated methods. The relationships for charge densities and multicenter–multielectron integrals obtained are valid for the arbitrary quantum numbers, screening constants, and location of Ψα-orbitals.

scholarly journals Does Emotional Value Play a Role in the Relationship between Risk and Loyalty?

2019 ◽  
Vol 2 (2) ◽  
pp. 35-42 ◽  
Author(s):  
Mircea-Andrei Scridon
Keyword(s):  
Perceived Risk ◽  
Structural Equation ◽  
Financial Risk ◽  
Future Research ◽  
Medium Size ◽  
Equation Modelling ◽  
Modelling Techniques ◽  
The One ◽  
Emotional Value ◽  
The Relationship

Abstract Although perceived value is considered essential in any marketing activity, the role it plays regarding the relationship between perceived risk and loyalty in the context of organizational markets is not thoroughly considered. Therefore, this paper addresses the aforementioned issues in the context of the small and medium size enterprise market in Romania. From a sample of 229 entities, data were collected and analysed using structural equation modelling techniques. Results confirmed that different relationships are established between functional or financial risk and emotional value on the one hand, and emotional value and loyalty on the other hand. Discussions of the results integrate main findings with other studies that partially or tangentially study the connections between emotional value, risk and loyalty. The paper end with a brief limitations and avenues for future research.

scholarly journals Evaluation of the one electron expectation values for different wave function of Be atom

2007 ◽  
Vol 4 (3) ◽  
pp. 393-396
Author(s):  
Baghdad Science Journal
Keyword(s):  
Wave Function ◽  
Slater Determinant ◽  
Open Shell ◽  
Expectation Values ◽  
Electronic Density ◽  
Expectation Value ◽  
Hartree Fock ◽  
Shell System ◽  
Electronic Wave Function ◽  
The One

The aim of this work is to evaluate the one- electron expectation value from the radial electronic density function D(r1) for different wave function for the 2S state of Be atom . The wave function used were published in 1960,1974and 1993, respectavily. Using Hartree-Fock wave function as a Slater determinant has used the partitioning technique for the analysis open shell system of Be (1s22s2) state, the analyze Be atom for six-pairs electronic wave function , tow of these are for intra-shells (K,L) and the rest for inter-shells(KL) . The results are obtained numerically by using computer programs (Mathcad).

scholarly journals Extended theoretical transition data in C i–iv

2021 ◽  
Vol 502 (3) ◽  
pp. 3780-3799
Author(s):  
W Li ◽  
A M Amarsi ◽  
A Papoulia ◽  
J Ekman ◽  
P Jönsson
Keyword(s):  
Transition Probabilities ◽  
Energy Levels ◽  
Oscillator Strengths ◽  
Atomic Data ◽  
Internal Validation ◽  
Hartree Fock ◽  
Relativistic Configuration ◽  
The Difference ◽  
The One ◽  
Relative Differences

ABSTRACT Accurate atomic data are essential for opacity calculations and for abundance analyses of the Sun and other stars. The aim of this work is to provide accurate and extensive results of energy levels and transition data for C i–iv. The Multiconfiguration Dirac–Hartree–Fock and relativistic configuration interaction methods were used in this work. To improve the quality of the wavefunctions and reduce the relative differences between length and velocity forms for transition data involving high Rydberg states, alternative computational strategies were employed by imposing restrictions on the electron substitutions when constructing the orbital basis for each atom and ion. Transition data, for example, weighted oscillator strengths and transition probabilities, are given for radiative electric dipole (E1) transitions involving levels up to 1s22s22p6s for C i, up to 1s22s27f for C ii, up to 1s22s7f for C iii, and up to 1s28g for C iv. Using the difference between the transition rates in length and velocity gauges as an internal validation, the average uncertainties of all presented E1 transitions are estimated to be 8.05 per cent, 7.20 per cent, 1.77 per cent, and 0.28 per cent, respectively, for C i–iv. Extensive comparisons with available experimental and theoretical results are performed and good agreement is observed for most of the transitions. In addition, the C i data were employed in a re-analysis of the solar carbon abundance. The new transition data give a line-by-line dispersion similar to the one obtained when using transition data that are typically used in stellar spectroscopic applications today.

scholarly journals A hydrometeorological model intercomparison as a tool to quantify the forecast uncertainty in a medium size basin

2008 ◽  
Vol 8 (4) ◽  
pp. 819-838 ◽  
Author(s):  
A. Amengual ◽  
T. Diomede ◽  
C. Marsigli ◽  
A. Martín ◽  
A. Morgillo ◽  
...  
Keyword(s):  
Large Scale ◽  
Mesoscale Model ◽  
Northern Italy ◽  
Precipitation Event ◽  
Medium Size ◽  
Hydrological Models ◽  
Model Intercomparison ◽  
Mesoscale Models ◽  
Prediction And Prevention ◽  
The One

Abstract. In the framework of AMPHORE, an INTERREG III B EU project devoted to the hydrometeorological modeling study of heavy precipitation episodes resulting in flood events and the improvement of the operational hydrometeorological forecasts for the prediction and prevention of flood risks in the Western Mediterranean area, a hydrometeorological model intercomparison has been carried out, in order to estimate the uncertainties associated with the discharge predictions. The analysis is performed for an intense precipitation event selected as a case study within the project, which affected northern Italy and caused a flood event in the upper Reno river basin, a medium size catchment in the Emilia-Romagna Region. Two different hydrological models have been implemented over the basin: HEC-HMS and TOPKAPI which are driven in two ways. Firstly, stream-flow simulations obtained by using precipitation observations as input data are evaluated, in order to be aware of the performance of the two hydrological models. Secondly, the rainfall-runoff models have been forced with rainfall forecast fields provided by mesoscale atmospheric model simulations in order to evaluate the reliability of the discharge forecasts resulting by the one-way coupling. The quantitative precipitation forecasts (QPFs) are provided by the numerical mesoscale models COSMO and MM5. Furthermore, different configurations of COSMO and MM5 have been adopted, trying to improve the description of the phenomena determining the precipitation amounts. In particular, the impacts of using different initial and boundary conditions, different mesoscale models and of increasing the horizontal model resolutions are investigated. The accuracy of QPFs is assessed in a threefold procedure. First, these are checked against the observed spatial rainfall accumulations over northern Italy. Second, the spatial and temporal simulated distributions are also examined over the catchment of interest. And finally, the discharge simulations resulting from the one-way coupling with HEC-HMS and TOPKAPI are evaluated against the rain-gauge driven simulated flows, thus employing the hydrological models as a validation tool. The different scenarios of the simulated river flows – provided by an independent implementation of the two hydrological models each one forced with both COSMO and MM5 – enable a quantification of the uncertainties of the precipitation outputs, and therefore, of the discharge simulations. Results permit to highlight some hydrological and meteorological modeling factors which could help to enhance the hydrometeorological modeling of such hazardous events. Main conclusions are: (1) deficiencies in precipitation forecasts have a major impact on flood forecasts; (2) large-scale shift errors in precipitation patterns are not improved by only enhancing the mesoscale model resolution; and (3) weak differences in flood forecasting performance are found by using either a distributed continuous or a semi-distributed event-based hydrological model for this catchment.

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