Semiempirical quantum chemical PM3 computations and evaluations of redox potentials, basicities, and dipole moments of the diphenylamine series as analytical reagents

1999 ◽  
Vol 77 (12) ◽  
pp. 2053-2058 ◽  
Author(s):  
Alexei N Pankratov ◽  
Andrew E Shchavlev
Keyword(s):  
Dipole Moment ◽  
Redox Potential ◽  
Quantum Chemical ◽  
Dipole Moments ◽  
Cooh Group ◽  
Redox Potentials ◽  
Proton Affinities ◽  
Chemical Evaluation ◽  
Analytical Reagents ◽  
Experimental Values

By evaluating the obtained results of PM3 computations, the following correlations were found: (i) the diarylamines redox potentials (E) with the first ionization potentials (I); (ii) the pKa values characterizing both the amines nitrogen protonation and the carboxy substituted reagents dissociation via the COOH group, with the proton affinities of the corresponding diphenylamines and COO--containing anions; (iii) the experimental values of the molecules dipole moments (μ) with the theoretical ones. The feasibility of the simple semiempirical quantum chemical evaluation of E, pKa, and μ of the diphenylamine series as redox reagents was determined.Key words: diphenylamine series, redox potential, pKa, dipole moment, semiempirical quantum chemical evaluation

Experimentelle und Quantenchemische Untersuchungen der Dipolmomente von Substituierten Stilbenen im Ersten Angercgten Singulettzustand / Experimental and Quantum Chemical Investigations of Dipole Moments of Substituted Stilbens in the First Excited Singlet State

1977 ◽  
Vol 32 (5) ◽  
pp. 420-425 ◽  
Author(s):  
A. Kawski ◽  
I. Gryczyński
Keyword(s):  
Dipole Moment ◽  
Excited States ◽  
Ground State ◽  
Quantum Chemical ◽  
Singlet State ◽  
Dipole Moments ◽  
Excited Singlet State ◽  
Excited Singlet ◽  
Fluorescent State ◽  
Experimental Values

Abstract The values a/a3 (α = polarizability), the Onsager cavity radii a and the dipole moments μe of six substituted stilbens in the fluorescent state have been determined. It is shown that if the dipole moment of the lowest excited singlet state μe is parallel to the dipole moment in the ground state μg, the values of μe and a can be determined from the solvent effects. Moreover, quantum chemical investigations of the dipole moments in the ground and excited states were carried out with the Pariser-Parr-Pople method and compared with the experimental values.

scholarly journals Role of redox-inactive metals in controlling the redox potential of heterometallic manganese–oxido clusters

2021 ◽  
Author(s):  
Keisuke Saito ◽  
Minesato Nakagawa ◽  
Manoj Mandal ◽  
Hiroshi Ishikita
Keyword(s):  
Photosystem Ii ◽  
Redox Potential ◽  
Quantum Chemical Calculations ◽  
Catalytic Reaction ◽  
Quantum Chemical ◽  
Ionic Radius ◽  
Redox Potentials ◽  
Oxygen Evolving ◽  
Highest Occupied Molecular Orbitals

AbstractPhotosystem II (PSII) contains Ca2+, which is essential to the oxygen-evolving activity of the catalytic Mn4CaO5 complex. Replacement of Ca2+ with other redox-inactive metals results in a loss/decrease of oxygen-evolving activity. To investigate the role of Ca2+ in this catalytic reaction, we investigate artificial Mn3[M]O2 clusters redox-inactive metals  [M] ([M]  = Mg2+, Ca2+, Zn2+, Sr2+, and Y3+), which were synthesized by Tsui et al. (Nat Chem 5:293, 2013). The experimentally measured redox potentials (Em) of these clusters are best described by the energy of their highest occupied molecular orbitals. Quantum chemical calculations showed that the valence of metals predominantly affects Em(MnIII/IV), whereas the ionic radius of metals affects Em(MnIII/IV) only slightly.

Experimental and computed dipole moments in donor–bridge–acceptor systems with p-phenylene and p-carboranediyl bridges

2009 ◽  
Vol 74 (1) ◽  
pp. 131-146 ◽  
Author(s):  
Ladislav Drož ◽  
Mark A. Fox ◽  
Drahomír Hnyk ◽  
Paul J. Low ◽  
J. A. Hugh MacBride ◽  
...  
Keyword(s):  
Dipole Moment ◽  
Dipole Moments ◽  
Electronic Effects ◽  
Electronic Interactions ◽  
Donor And Acceptor ◽  
Homo And Lumo ◽  
Pull Systems ◽  
The Difference ◽  
Experimental Values ◽  
2D And 3D

Dipole moments were measured for a series of substituted benzenes, biphenyls, terphenyls, C-monoaryl- and C,C′-diaryl-p-carboranes. For the donor–bridge–acceptor systems, Me2N–X–NO2, where X is 1,4-phenylene, biphenyl-4,4′-diyl, terphenyl and 1,4-C6H4-p-CB10H10C-1,4-C6H4, the measured interaction dipole moments are 1.36, 0.74, 0.51 and 0.00 D, respectively. The magnitude of the dipole moment reflects the ability of the bridge to transmit electronic effects between donor and acceptor groups. Thus, whilst the 1,4-phenylene bridges allow moderate electronic interactions between the remote groups, the p-carboranediyl unit is less efficient as a conduit for electronic effects. Averaged dipole moments computed at the DFT (B3LYP/6-31G*) level of theory from two distinct molecular conformers are in good agreement with the experimental values. Examination of the calculated electronic structures provides insight into the nature of the interactions between the donor and acceptor moieties through these 2D and 3D aromatic bridges. The most significant cooperative effect of the bridge on the dipole moment occurs in systems where there is some overlap between the HOMO and LUMO orbitals. This orbital overlap criterion may help to define the difference between “push-pull” systems in which electronic effects are mediated by the bridging moiety, and simpler systems in which the bridge acts as an electronically innocent spacer unit and through-space charge transfer/separation is dominant.

The Electrostatic Moments of a Charge Distribution

1997 ◽  
Author(s):  
Philip Coppens
Keyword(s):  
Dipole Moment ◽  
Charge Distribution ◽  
Dipole Moments ◽  
Practical Importance ◽  
Diffraction Method ◽  
Quadrupole Moments ◽  
Charge Densities ◽  
Moment Vector ◽  
Experimental Values ◽  
A Charge

The moments of a charge distribution provide a concise summary of the nature of that distribution. They are suitable for quantitative comparison of experimental charge densities with theoretical results. As many of the moments can be obtained by spectroscopic and dielectric methods, the comparison between techniques can serve as a calibration of experimental and theoretical charge densities. Conversely, since the full charge density is not accessible by the other experimental methods, the comparison provides an interpretation of the results of the complementary physical techniques. The electrostatic moments are of practical importance, as they occur in the expressions for intermolecular interactions and the lattice energies of crystals. The first electrostatic moment from X-rays was obtained by Stewart (1970), who calculated the dipole moment of uracil from the least-squares valence-shell populations of each of the constituent atoms of the molecule. Stewart’s value of 4.0 ± 1.3 D had a large experimental uncertainty, but is nevertheless close to the later result of 4.16 ± 0.4 D (Kulakowska et al. 1974), obtained from capacitance measurements of a solution in dioxane. The diffraction method has the advantage that it gives not only the magnitude but also the direction of the dipole moment. Gas-phase microwave measurements are also capable of providing all three components of the dipole moment, but only the magnitude is obtained from dielectric solution measurements. We will use an example as illustration. The dipole moment vector for formamide has been determined both by diffraction and microwave spectroscopy. As the diffraction experiment measures a continuous charge distribution, the moments derived are defined in terms of the method used for space partitioning, and are not necessarily equal. Nevertheless, the results from different techniques agree quite well. A comprehensive review on molecular electric moments from X-ray diffraction data has been published by Spackman (1992). Spackman points out that despite a large number of determinations of molecular dipole moments and a few determinations of molecular quadrupole moments, it is not yet widely accepted that diffraction methods lead to valid experimental values of the electrostatic moments.

scholarly journals Calculating transition dipole moments of phosphorescent emitters for efficient organic light-emitting diodes

2019 ◽  
Vol 21 (19) ◽  
pp. 9740-9746
Author(s):  
Mohammad Babazadeh ◽  
Paul L. Burn ◽  
David M. Huang
Keyword(s):  
Dipole Moment ◽  
Quantum Chemical ◽  
Dipole Moments ◽  
Molecular Geometry ◽  
Transition Dipole Moment ◽  
Organic Light Emitting Diodes ◽  
Transition Dipole ◽  
Light Emitting ◽  
Organic Light ◽  
Transition Dipole Moments

Quantum-chemical calculations show that the direction of the transition dipole moment of organometallic phosphorescent emitters is sensitive to molecular geometry.

Dielectric properties of hexafluoroacetone and hexachloroacetone

1969 ◽  
Vol 47 (12) ◽  
pp. 2253-2256 ◽  
Author(s):  
R. K. Chan
Keyword(s):  
Dipole Moment ◽  
Dielectric Properties ◽  
Liquid State ◽  
Dipole Moments ◽  
Dielectric Constants ◽  
Pure Liquid ◽  
Gaseous State ◽  
Vector Addition ◽  
Inductive Effects ◽  
Experimental Values

The dielectric constants of hexafluoro- and hexachloro-acetone are measured in the solid and liquid state. They show negligible association in the liquid state. The dipole moments are 0.648 D measured in the gaseous state and 0.63 D in pure liquid for hexafluoroacetone, and 1.24 D in carbon tetrachloride solution and 1.34 D in pure liquid for hexachloroacetone. If the differences between inductive effects due to CX3 and C=O groups can be ignored, the vector addition of bond moments gives values of dipole moment which are compatible with the experimental values.

Configuration and Conformation Study of S-Allyl O-Methyl N-(2- and 4-Substituted Acridin-9-yl)thiocarbonimidates in Relation to Their [3,3] Sigmatropic Rearrangement

1998 ◽  
Vol 63 (3) ◽  
pp. 387-393 ◽  
Author(s):  
Ivan Danihel ◽  
Kalevi Pihlaja ◽  
Ján Imrich ◽  
Gejza Suchár ◽  
Pavol Kristian ◽  
...  
Keyword(s):  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Dipole Moments ◽  
Chair Conformation ◽  
Sigmatropic Rearrangement ◽  
Difference Spectra ◽  
Vector Addition ◽  
Chloro Derivatives ◽  
Experimental Values ◽  
Configuration And Conformation

Configuration and conformations of S-allyl O-methyl N-(2- and 4-substituted acridin-9-yl)thiocarbonimidates were studied by means of NMR spectroscopy, dipole moments and quantum chemical calculations. The E configuration was proved for the unsubstituted and 2-chloro derivatives from the NOE-difference spectra. Experimental values of dipole moments were related to those obtained from vector addition. Quantum chemical calculations pointed to the chair conformation of these compounds in transition state for above-mentioned rearrangement.

π-Elektronen-Dipolmoment eines Pyridinium-N-phenol-betains

1966 ◽  
Vol 21 (9) ◽  
pp. 1373-1376 ◽  
Author(s):  
A. Schweig ◽  
C. Reichardt
Keyword(s):  
Dielectric Constant ◽  
Dipole Moment ◽  
Ground State ◽  
Dipole Moments ◽  
Saturated Hydrocarbon ◽  
Dilute Solution ◽  
Uniform Medium ◽  
Order Of Magnitude ◽  
Dimensional Electron Gas ◽  
Experimental Values

The ground state dipole moment of the π-electrons of 2.4.6-triphenyl-N- [3.5-di-tert-butyl-4-hydroxy-phenyl] -pyridinium-betain I, a highly solvatochromic substance, was determined by measuring the dielectric constant of a dilute solution and calculating first the dipole moment of the whole system (σ- and π-electrons) using the method of HALVERSTADT and KUMLER. The dipole moment of the π-electrons was then calculated, asuming the π-electron dipole to be imbedded in a spherical medium of dielectric constant 2. The value calculated by this method was compared with the π-electron dipole moment directly obtained from the dielectric constant of the dilute solution using a method of H. KUHN. This method is based on the assumption that a π-electron of a dissolved molecule sees the σ-electrons of the molecule and of the surrounding solvent, a saturated hydrocarbon, as a continuous uniform medium of dielectric constant 2. Thus the π-electron dipole of the solute molecule is regarded as being imbedded in a continuous medium of dielectric constant 2. It was found that the values of the π-electron dipole moments determined by the two methods agree well. Furthermore these experimental values agree with a theoretical value obtained in the case of N- [4-hydroxy-phenyl] -pyridinium-betain II using the one dimensional electron gas method including electron repulsion. The order of magnitude of the π-electron dipole moment of I clearly shows that the ground state of this molecule is highly polar.

Quantum chemical study of sulfonium ylides: Structure, charge distribution and dipole moments

1980 ◽  
Vol 45 (4) ◽  
pp. 1236-1250 ◽  
Author(s):  
Vladimír Král ◽  
Zdeněk Arnold ◽  
Václav Jehlička ◽  
Otto Exner
Keyword(s):  
Ab Initio ◽  
Charge Distribution ◽  
Quantum Chemical ◽  
Dipole Moments ◽  
Quantum Chemical Study ◽  
Chemical Study ◽  
Quantum Chemical Methods ◽  
Sulfonium Ylide ◽  
Experimental Values ◽  
Sulfonium Ylides

The geometry, charge distribution and dipole moments of parent sulfonium ylide - dimethylsulfoniomethylide (I) - and a series of stabilized sulfonium ylides, including 2-dimethylsulfuranylidene-1,3-cyclopentanedione (VI) prepared in this study, was investigated using the CNDO/2, PCILO and ab initio methods. Values of dipole moments, calculated by quantum chemical methods (CNDO/2 with sp and spd bases, ab initio with the STO-3G basis) as well as by the method of empirical bond moments, are compared with the experimental values determined in dioxane or benzene. Dipole moments of several related ammonium ylides were also studied.

Vibrational Dynamics of the H2O . HF Complex. Potential Energy and Electric Dipole Moment Surfaces

1993 ◽  
Vol 58 (12) ◽  
pp. 2813-2830 ◽  
Author(s):  
Andrzej J. Sadlej ◽  
Ota Bludský ◽  
Vladimír Špirko
Keyword(s):  
Dipole Moment ◽  
Potential Energy ◽  
Electric Dipole Moment ◽  
Electric Dipole ◽  
Vibrational Energy ◽  
Dipole Moments ◽  
Energy Levels ◽  
Equilibrium Geometry ◽  
Two Dimensional ◽  
Experimental Values

A total of 330 points on the potential energy and electric dipole moment surfaces of the ground electronic state of the H2O . HF complex have been calculated ab initio using the SCF method and many-body perturbation theory (MBPT). To keep the calculations manageable, the geometry parameters of H2O were fixed at their experimental values and only certain two dimensional sections of the total surfaces have been evaluated. for each of the two-dimensional surface section, analytic potential energy and electric dipole moment functions have been fitted through the points and corresponding vibrational energy levels and effective electric dipole moments have been calculated using approximate vibrational Hamiltonians. The calculated values of resulting vibrational energies and effective electric dipoles from differently wide intervals for different vibrational modes. The intervals corresponding to the most interesting low frequency modes (out-of-plane and H2O vs HF stretching) are very narrow and coincide satisfactory with the corresponding experimental values. A very reasonable agreement has also been obtained for the equilibrium geometry, electric dipole moment and dissociation energy De of the complex. These findings lead us to believe that the calculated potential energy and electric dipole moment surfaces are sufficiently accurate for predicting purposes and rationalization of the so far unassigned spectral data of H2O . HF.

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