DFT-based chemical reactivity indices in the Hartree-Fock method. II. Fukui function, chemical potential, and hardness

2005 ◽  
Vol 123 (12) ◽  
pp. 124103 ◽  
Author(s):  
Robert Balawender ◽  
Paul Geerlings
Keyword(s):  
Chemical Potential ◽  
Chemical Reactivity ◽  
Fukui Function ◽  
Hartree Fock ◽  
Reactivity Indices

scholarly journals Anticancer Indole-Based Chalcones: A Structural and Theoretical Analysis

Molecules ◽  
2019 ◽  
Vol 24 (20) ◽  
pp. 3728 ◽  
Author(s):  
Farid A. Badria ◽  
Saied M. Soliman ◽  
Saleh Atef ◽  
Mohammad Shahidul Islam ◽  
Abdullah Mohammed Al-Majid ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Theoretical Analysis ◽  
Dft Calculations ◽  
Density Functional ◽  
Chemical Potential ◽  
Chemical Reactivity ◽  
Stacking Interactions ◽  
Functional Theory ◽  
Topology Analysis ◽  
Reactivity Indices

The crystal structures of five new chalcones derived from N-ethyl-3-acetylindole with different substituents were investigated: (E)-3-(4-bromophenyl)-1-(1-ethyl-1H-indol-3-yl)prop-2-en-1-one (3a); (E)-3-(3-bromophenyl)-1-(1-ethyl-1H-indol-3-yl)prop-2-en-1-one (3b); (E)-1-(1-ethyl-1H-indol-3-yl)-3-(4-methoxyphenyl)prop-2-en-1-one (3c); (E)-1-(1-ethyl-1H-indol-3-yl)-3-mesitylprop-2-en-1-one (3d); and (E)-1-(1-ethyl-1H-indol-3-yl)-3-(furan-2-yl)prop-2-en-1-one (3e). The molecular packing of the studied compounds is controlled mainly by C–H⋅⋅⋅O hydrogen bonds, C–H⋅⋅⋅π interactions, and π···π stacking interactions, which were quantitatively analyzed using Hirshfeld topology analysis. Using density functional theory (DFT) calculations, the order of polarity (3b ˂ 3d ˂ 3e ˂ 3a ˂ 3c) was determined. Several chemical reactivity indices such as the ionization potential (I), electron affinity (A), chemical potential (μ), hardness (η), electrophilicity (ω) and nucleophilicity (N) indices were calculated, and these properties are discussed and compared. In addition, the antiproliferative activity of the five new chalcones was studied.

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).

Effect of aqueous environment in chemical reactivity of monolignols. A New Fukui Function Study

2009 ◽  
Vol 28 (2) ◽  
pp. 196-201 ◽  
Author(s):  
Carmen Martínez ◽  
Miriam Sedano ◽  
Jorge Mendoza ◽  
Rafael Herrera ◽  
Jose G. Rutiaga ◽  
...  
Keyword(s):  
Chemical Reactivity ◽  
Fukui Function ◽  
Aqueous Environment ◽  
Function Study

scholarly journals Experimental and theoretical studies on the photodegradation of 2-ethylhexyl 4-methoxycinnamate in the presence of reactive oxygen and chlorine species

2014 ◽  
Vol 12 (5) ◽  
pp. 612-623 ◽  
Author(s):  
Alicja Gackowska ◽  
Maciej Przybyłek ◽  
Waldemar Studziński ◽  
Jerzy Gaca
Keyword(s):  
Experimental Studies ◽  
Fukui Function ◽  
Mass Spectrometric ◽  
Theoretical Studies ◽  
Reaction Products ◽  
Reactivity Indices ◽  
Mass Spectrometric Detector ◽  
Methoxycinnamic Acid ◽  
Experimental And Theoretical Studies ◽  
Dft And Mp2 Calculations

Abstract2-Ethylhexyl 4-methoxycinnamate (EHMC) is one of the most commonly used sunscreen ingredient. In this study we investigated photodegradation of EHMC in the presence of such common oxidizing and chlorinating systems as H2O2, H2O2/HCl, H2O2/UV, and H2O2/HCl/UV. Reaction products were detected by gas chromatography with a mass spectrometric detector (GC-MS). As a result of experimental studies chloro-substituted 4-methoxycinnamic acid (4-MCA), 4-methoxybenzaldehyde (4-MBA) and 4-methoxyphenol (4-MP) were identified. Experimental studies were enriched with DFT and MP2 calculations. We found that reactions of 4-MCA, 4-MBA and 4-MP with Cl2 and HOCl were in all cases thermodynamically favorable. However, reactivity indices provide a better explanation of the formation of particular chloroorganic compounds. Generally, those isomeric forms of mono- and dichlorinated compounds which exhibits the highest hardness were identified. Nucleophilicity of the chloroorganic compounds precursors were examined by means of the Fukui function.

scholarly journals Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes

Molecules ◽  
2020 ◽  
Vol 25 (18) ◽  
pp. 4043 ◽  
Author(s):  
Temiloluwa T. Adejumo ◽  
Nikolaos V. Tzouras ◽  
Leandros P. Zorba ◽  
Dušanka Radanović ◽  
Andrej Pevec ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Gas Phase ◽  
Molecular Orbital ◽  
Density Functional ◽  
Chemical Potential ◽  
Chemical Reactivity ◽  
Geometry Optimization ◽  
Coupling Reaction ◽  
Functional Theory ◽  
Reactivity Descriptors

Two new Zn(II) complexes with tridentate hydrazone-based ligands (condensation products of 2-acetylthiazole) were synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction methods. The complexes 1, 2 and recently synthesized [ZnL3(NCS)2] (L3 = (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex 3 were tested as potential catalysts for the ketone-amine-alkyne (KA2) coupling reaction. The gas-phase geometry optimization of newly synthesized and characterized Zn(II) complexes has been computed at the density functional theory (DFT)/B3LYP/6–31G level of theory, while the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) energies were calculated within the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G and B3LYP/6-311G(d,p) levels of theory. From the energies of frontier molecular orbitals (HOMO–LUMO), the reactivity descriptors, such as chemical potential (μ), hardness (η), softness (S), electronegativity (χ) and electrophilicity index (ω) have been calculated. The energetic behavior of the investigated compounds (1 and 2) has been examined in gas phase and solvent media using the polarizable continuum model. For comparison reasons, the same calculations have been performed for recently synthesized [ZnL3(NCS)2] complex 3. DFT results show that compound 1 has the smaller frontier orbital gap so, it is more polarizable and is associated with a higher chemical reactivity, low kinetic stability and is termed as soft molecule.

scholarly journals Analysis of the Gas Phase Acidity of Substituted Benzoic Acids Using Density Functional Concepts

Molecules ◽  
2020 ◽  
Vol 25 (7) ◽  
pp. 1631
Author(s):  
Jorge A. Amador-Balderas ◽  
Michael-Adán Martínez-Sánchez ◽  
Ramsés E. Ramírez ◽  
Francisco Méndez ◽  
Francisco J. Meléndez
Keyword(s):  
Gas Phase ◽  
Density Functional ◽  
Chemical Potential ◽  
Fukui Function ◽  
Ortho Position ◽  
Benzoic Acids ◽  
Functional Theory ◽  
Resonance Effects ◽  
Gas Phase Acidity ◽  
Substituted Benzoic Acids

A theoretical study of the effect of the substituent Z on the gas phase acidity of substituted benzoic acids ZC6H4COOH in terms of density functional theory descriptors (chemical potential, softness and Fukui function) is presented. The calculated gas phase ΔacidG° values obtained were close to the experimental ones reported in the literature. The good relationship between the ΔacidG° values and the electronegativity of ZC6H4COOH and its fragments, suggested a better importance of the inductive than polarizability contributions. The balance of inductive and resonance contributions of the substituent in the acidity of substituted benzoic acids showed that the highest inductive and resonance effects were for the -SO2CF3 and -NH2 substituents in the para- and ortho-position, respectively. The Fukui function confirmed that the electron-releasing substituent attached to the phenyl ring of benzoic acid decreased the acidity in the trend ortho > meta > para, and the electron-withdrawing substituent increased the acidity in the trend ortho < meta < para.

Local chemical potential, local hardness, and dual descriptors in temperature dependent chemical reactivity theory

2017 ◽  
Vol 19 (21) ◽  
pp. 13687-13695 ◽  
Author(s):  
Marco Franco-Pérez ◽  
Paul W. Ayers ◽  
José L. Gázquez ◽  
Alberto Vela
Keyword(s):  
Chemical Potential ◽  
Chemical Reactivity ◽  
Potential Well ◽  
Temperature Dependent ◽  
Local Hardness ◽  
Chemical Reactivity Theory ◽  
Definition Of

From the definition of a local chemical potential, well-behaved expressions for the local hardness and the dual descriptors are derived.

Sign in / Sign up

Export Citation Format

Share Document