Some INDO calculations of fluorine-nitrogen spin–spin coupling constants

INDO parameterized calculations of ⁿJ(¹⁹F¹⁵N) are reported where n=1, 2, 3, 4 and 5. The calculations are performed within the sum-over-states perturbation and self-consistent perturbation frameworks. In general, satisfactory agreement between both sets of calculated results and the available experimental data is obtained. All of the ¹ J(¹⁹F¹⁵N) and ⁴J(¹⁹F¹⁵N) couplings can be of either sign. Most of the couplings considered are dominated by the contact contribution but the non-contact interactions can be very important in certain cases.     

The stereochemical dependence of one-bond carbon-carbon coupling constants

Spin-spin coupling constants for carbon-carbon single bonds vary with the orientation of lone pairs on adjacent nitrogen atoms and of adjacent carbonyl groups.     

Some INDO perturbation calculations of nJ(NC) values

Standard INDO parameters are used in ‘sum-over-states’ perturbation calculations of ⁿJ(NC) in a variety of molecular environments. Good agreement with the experimental data is, in general, obtained when the integral products S_N²(o)S_C²(o) and 〈r^?3〉_N〈r^?3〉_C assume the values of 35.167 a.u.^?3 and 4.980 a.u.^?3, respectively. For ‘pyridine-type’ nitrogen atoms the major contribution to ⁿJ(NC) usually arises from the orbital term whereas the contact term dominates the values of ⁿJ(NC) for ‘pyrrole-type’ and amino nitrogen atoms.     

INDO calculations of the solvent dependence of some spin–spin couplings of fluorocarbons

The results of some SCPT and SOS calculations of ¹J(CH), ¹J(FC), ²J(FH), ³J(FH), ³J(FF) and ¹J(CC) in a variety of solvents are reported. The calculations employ the solvaton model and INDO parameters. In almost all cases the coupling is predicted to increase as the dielectric constant of the solvent increases, the exception being ³J(FH)cis in trifluoroethylene which is supported by experimental results.     

Note of the INDO geometry optimization of biphenyl

Recently published results of Rayez and Dannenberg concerning the biphenyl molecule show some inadequacies. Our recalculation gives contrary results, which are in qualitatively good agreement with some CNDO/2 calculations presented recently. Consequently, implictions discussed by Rayez and Dannenberg are not justified and they are in contrast to our experience with CNDO/2 geometry optimizations.     

Unrestricted Hartree-Fock instabilities in semiempirical CNDO/S and INDO/S calculations of spin-spin coupling constants

It is shown that non-convergent calculations of the Fermi contact term of spin-spin coupling constants within the self-consistent and finite perturbation schemes used to solve the coupled Hartree-Fock equations, are originated in non-singlet Hartree-Fock instabilities of the closed-shell restricted Hartree-Fock wavefunction. In CNDO/S and INDO/S wavefunctions, where the electronic system response has been successfully reproduced, all investigated molecules containing MOs were found to be unstable. Results of spin-spin coupling constants are given and compared with experimental as well as FP and SOS INDO values.Part of a Ph.D. thesis (G.E.S.) to be presented to the University of Buenos Aires.Comisión de Investigaciones Científicas (CIC, Pcia. de Bs. As.) fellow.     

Solvent dependence on conformational transition, dipole moment, and molecular geometry of 1,2-dichloroethane: insight from Car-Parrinello molecular dynamics calculations

We have investigated the molecular geometry and dipole moment distribution for the major conformational states of 1,2-dichloroethane (DCE) in three different solvents under ambient conditions using the Car-Parrinello mixed quantum mechanics/molecular mechanics method. The solvents studied were water, DCE, and chloroform. Within the time scale investigated, we find a conformational equilibrium existing between the gauche and trans forms of DCE in all three solvents. In the chloroform solvent, the conformational transition occurs more frequently than in water solvent and in liquid DCE (i.e., DCE solute in DCE solvent). The population of gauche conformer is more in the case of water solvent, while the trans conformer dominates in chloroform solvent. We report a bimodal nature of the dipole moment distribution for DCE in all three solute-solvents studied, where the peaks are attributed to the trans and gauche conformational states. The dipole moments of both of the conformational states increase with increasing polarity of the solvent. Also, with an increase in solvent polarity, an increase in the C-Cl bond length and magnitude of atomic charges in DCE has been observed. The increase in atomic charges of DCE is almost twice when the solvent is changed from chloroform to water.     

INDO-SCPT calculations of the solvent dependence of some carbon-proton spin-spin coupling constants

Summary A theoretical study of the effects of non-specific solute-solvent interactions on the directly bonded carbon-proton couplings¹ J(C–H), in acetaldehyde, acetone and acrylonitrile is presented. The solvent induced changes in these couplings calculated by an INDO-SCPT procedure incorporating a modified solvaton model are in satisfactory agreement with experiment and show significant improvement over the INDO-FPT calculations using the Klopman-Germer solvaton model.

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INDO-SCPT-Rechnungen der Lösungsmittelabhängigkeit einiger C-H-Kopplungskonstanten

Zusammenfassung Es wird eine theoretische Studie zu den nichtspezifischen Lösungsmittelwechselwirkungen auf die Spin-Spin-Kopplungen direkt aneinander gebundener C- und H-Atome von Acetaldehyd, Aceton und Acrylnitril vorgestellt. Die vom Solvens induzierten Änderungen der Kopplungskonstanten werden von der INDO-SCPT-Methode unter Verwendung eines modifizierten Solvationsmodells zufriedenstellend wiedergegeben. Die Übereinstimmung mit den experimentellen Daten ist besser als INDO-FPT-Rechnungen mit dem Klopmann-Germer-Solvaton-Modell.

     

Stereoelectronic interactions and the one-bond C-F coupling constant in sevoflurane

The conformational preference of the widely utilized anesthetic fluoromethyl-1,1,1,3,3,3-hexafluoro-2-propyl ether (sevoflurane) has been investigated computationally and by NMR spectroscopy. Three conformational minima were located at the B3LYP/aug-cc-pVDZ level, but one is significantly more stable (by ca. 4 kcal/mol) than the other two. This is the case both for gas phase calculations and for solution NMR data. Although the main conformer is stabilized by electron delocalization (n(O) → σ*(C-F)), this type of hyperconjugation was not found to be the main driver for the conformer stabilization in the gas phase and, consequently, for the apparent anomeric effect in sevoflurane. Instead, more classical steric and electrostatic interactions appear to be responsible for the conformational energies. Also the (1)J(CF) coupling constants do not appear to be dominated by hyperconjugation; again, dipolar interactions are invoked instead.     

Some INDO calculations of 1J(PC) and 1J(PF) values

INDO parameterized calculations, employing phosphorus s, p and d valence orbitals, are reported for values of ¹J(PC) and ¹J(PF) relating to phosphorus in formal tri- and pentavalent states. The ¹J(PC), interactions are mainly controlled by the contact term. Thus, trivalent phosphorus compounds have negative values for ¹J(PC), whereas those for pentavalent phosphorus are positive due to the s lone-pair effect. The inclusion of phosphorus 3d orbitals is shown to be important for an understanding of the processes contributing to ¹J(PF) interactions. ¹J(PF) values are shown to be negative for both tri- and pentavalent phosphorus compounds. The contact and orbital interactions are significant for the trivalent phosphorus molecules, whereas in the pentavalent phosphorus case ¹J(PF) is dominated by the orbital term.     

Quantum chemical calculations of fluoroethylene molecules by the CNDO and INDO methods

Conclusions A quantum chemical calculation of seven fluoroethylene molecules and two fluorochloroethylene molecules and two fluorochloroethylene molecules by the CNDO and INDO methods has made it possible to explain the experimentally observed change in reactivity and direction of addition reactions at the double bond. The data of a calculation of the relative stability of various isomers also agree with the experimental results.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2199–2202, October, 1973.     

Semi-empirical molecular orbital calculations the electronic structure and the spin-orbit coupling in azabenzenes

Electronic structures of pyridine, pyrazine, pyrimidine and pyridazine are studied by a semiempirical SCF method for valence electron systems previously proposed by the present authors. The charge distributions, transition energies and oscillator strengths of these compounds are calculated. The calculated results show fairly good agreement with the observed ones. Using these results, we have further calculated the oscillator strengths of singlet-triplet transitions and the life times of the triplet states (). In this treatment, we have considered the mixing of various singlets with T ₁ and triplets with S ₀, and the effect of -electrons is studied.

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Zusammenfassung Es werden nach einer von den Autoren dieser Arbeit vorgeschlagenen Methode die Elektronenstrukturen von Pyridin, Pyrazin, Pyrimidin und Pyridazin studiert. Die halbempirische SCF-Methode für Valenzelektronensysteme gestattet die Berechnung der Ladungsverteilungen, Übergangsenergien und Oszillatorstärken, die in recht guter Übereinstimmung mit der Beobachtung stehen. Ferner werden die Oszillatorstärken von Singulett-Triplett-Übergängen und die Lebensdauer von Triplett-Zuständen () berechnet.

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Résumé Les structures électroniques de la pyridine, de la pyrazine, de la pyrimidine et de la pyridazine sont étudiées par une méthode SCF semiempirique pour les électrons de valence proposée précédemment par les auteurs. Les distributions de charge, les énergies de transition et les forces oscillatrices de ces composés sont calculées, donnant des résultats en bon accord avec l'expérience. De plus nous avons calculé les forces oscillatrices des transitions singulet-triplet et les durées de vie des états triplets (). Dans ce calcul nous avons inclus l'interaction de configuration et l'étude de l'effet des électrons .

     

Influence of the INDO parameterization on the indirect spin–spin coupling constants as calculated by the FPT INDO method

Alterations have been introduced in the semi-empirical INDO parameters in order to study their influence on the Fermi contact term of the indirect spin–spin coupling constants as calculated by the finite perturbation theory (FPT). For this purpose a set of molecules containing hydrogen, carbon and/or fluorine has been selected. In general, most coupling constants are found to be much more sensitive than other molecular properties to small changes in the INDO parameters. This sensitivity depends strongly on the particular calculated coupling constant. In most cases the uncertainty in the INDO parameters leads to uncertainties in the coupling constants which are much greater than their experimental errors.     

CNDO,INDO and RCNDO-CI calculations on the electronic spectra of saturated hydrocarbons

CNDO, INDO and RCNDO (CNDO including higher (Rydberg) atomic orbitals in the basis) calculations completed by first order configuration interaction were performed on straight chain and branched chain paraffins.The results interpret reasonably the main characteristics of the observed electronic spectra. The importance of outer atomic orbitals is stressed and it is found that the first singlet-singlet transition of highly branched paraffins leads to an excited state with considerable Rydberg character.

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Zusammenfassung Rechnungen vom Typ CNDO, INDO und RCNDO (CNDO mit höheren (Rydberg) Atomorbitalen in der Basis) unter Einschluß von Konfigurationswechselwirkung 1. Ordnung wurden für unverzweigte und verzweigte gesättigte Kohlenwasserstoffe durchgeführt.Die Resultate lassen eine Deutung der Hauptcharakteristika der beobachteten Elektronen-spektren zu. Die Wichtigkeit der äußeren Atomorbitale ist zu betonen. Die ersten Singulett-Singulett-Übergänge der stark verzweigten Paraffine führen zu angeregten Zuständen mit beträchtlichem Rydbergcharakter.

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Résumé Des calculs CNDO, INDO et RCNDO (ayant des orbitales atomiques supérieures dans la base) ont été effectués sur les paraffines normales et ramifiées tenant compte de l'intéraction de configuration de premier ordre jusqu'à 30 configurations.Les résultats interprêtent d'une manière raisonnable les spectres électroniques mesurés. L'importance des orbitales atomiques supérieures apparaît clairement. La première bande observée des hydrocarbures hautement ramifiés comme le néopentane ou l'isobutane est attribuée à une transition dont l'état excité possède un fort caractère Rydberg.

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The research for this paper was supported in part by the Defense Research Board of Canada; Grant Number 9530-63.     

Understanding the dependence of the transitional properties of liquid crystal dimers on their molecular geometry

The characteristic feature of liquid crystal dimers, in which two mesogenic groups are linked by a flexible spacer, is often thought to be the strong odd-even effect exhibited by their transitional properties. That is, the nematic-isotropic transition temperature and the entropy of transition are large for dimers with an even number of groups in the spacer in comparison with those for neighbouring dimers with an odd number of groups. However, the magnitude of the odd-even effect along a homologous series of dimers is found to depend strongly on the nature of the link between the mesogenic group and the spacer. This dependence is thought to originate in the variation of the molecular geometry with the linking group, a view which is supported by detailed molecular field theory calculations involving all of the conformational states. Here we are concerned with developing a more transparent understanding of this geometrical effect using a simple model of the dimers in which all of the conformational states are replaced by just two, a linear and a bent conformer. The model has been found to exhibit a strong odd-even effect as well as a nematic-nematic transition when the bond angle is tetrahedral. We have used this model to explore the dependence of the transitional properties of liquid crystal dimers on their geometry by varying the bond angle of the bent conformer. The behaviour predicted by the model for the nematic-isotropic transition is found to be in qualitative agreement with experiment. In addition, the nematic-nematic transition is observed to exhibit a critical behaviour as the bond angle is increased. At the other extreme, when the bond angle is reduced to its limiting value of 90° there is a very strong first order transition between a discotic and a calamitic nematic.     

Some INDO/S?SOS calculations of the effects of hydrogen bonding on the nitrogen shielding of some heterocycles

Some INDO/S parameterized SOS shielding calculations are reported for the nitrogen nuclei of some N-heterocycles. Hydrogen bonding with H₂O and CF₃CH₂OH is incorporated in a supermolecule approach. The calculated effects of hydrogen bonding are found to be in satisfactory agreement with observed nitrogen shielding variations upon a change of solvent.     

INDO MO calculations of the electronic structures of pyrolle,imidazole, and derivatives

INDO MO calculations on a series of N-substituted pyrroles and imidazoles have been analysed for substituent effects. Some of the basic characteristics of the σ_I and σ_R⁰ parameters are reflected in the calculated electron densities of the compounds studied. For example, good correlations are obtained between Δqσ ^N(1)/ΣΔqσ parameters and σ_I for the R substituted compounds, as well as between ΣΔqπ values and σ_R⁰ for the + R derivatives. The + R substituents lead to an increased localization of the π-bonds, whereas R substituted derivatives show an increased delocalization, i.e., the π-bond orders across C(2)C(3) [or C(2)N(3)] and C(4)C(5) decrease and those across other bonds in the ring increase.     

Efficient and accurate approximations to the molecular spin-orbit coupling operator and their use in molecular g-tensor calculations

Approximations to the Breit-Pauli form of the spin-orbit coupling (SOC) operator are examined. The focus is on approximations that lead to an effective quasi-one-electron operator which leads to efficient property evaluations. In particular, the accurate spin-orbit mean-field (SOMF) method developed by Hess, Marian, Wahlgren, and Gropen is examined in detail. It is compared in detail with the "effective potential" spin-orbit operator commonly used in density functional theory (DFT) and which has been criticized for not including the spin-other orbit (SOO) contribution. Both operators contain identical one-electron and Coulomb terms since the SOO contribution to the Coulomb term vanishes exactly in the SOMF treatment. Since the DFT correlation functional only contributes negligibly to the SOC the only difference between the two operators is in the exchange part. In the SOMF approximation, the SOO part is equal to two times the spin-same orbit contribution. The DFT exchange contribution is of the wrong sign and numerically shown to be in error by a factor of 2-2.5 in magnitude. The simplest possible improvement in the DFT-SOC treatment [Veff(-2X)-SOC] is to multiply the exchange contribution to the Veff operator by -2. This is verified numerically in calculations of molecular g-tensors and one-electron SOC constants of atoms and ions. Four different ways of handling the computationally critical Coulomb part of the SOMF and Veff operators are discussed and implemented. The resolution of the identity approximation is virtually exact for the SOC with standard auxiliary basis sets which need to be slightly augmented by steep s functions for heavier elements. An almost as efficient seminumerical approximation is equally accurate. The effective nuclear charge model gives results within approximately 10% (on average) of the SOMF treatment. The one-center approximation to the Coulomb and one-electron SOC terms leads to errors on the order of approximately 5%. Small absolute errors are obtained for the one-center approximation to the exchange term which is consequently the method of choice [SOMF(1X)] for large molecules.