Influence de la Structure de Diverses Fonctions sur l'Evaluation de l'Energie de Correlation

The influence of various correlation functions, multiplying the monoelectronic space function, is studied and applied to the Helium atom and its isoelectronic series. We used Slater-type basis orbitals and the ground and first excited states have been studied, taking into account the virial and cusp conditions. In the ground state, a very good value for the correlation energy is obtained, using a function of the type For the excited states, this type of function overestimates the assumed value of the correlation energy.     

Détermination de l'énergie de conjugaison des acides naphtoǐques

The present paper deals with the experimental and theoretical determination of energies of conjugation of organic molecules.A computation process has been applied, first to simple molecules comprising an hydrocarbon (styrene), an oxygen function (benzaldehyde) and a nitrogen function (aniline). The results are compared with those obtained from the literature.The application of this computation process to naphthoic acids permits the determination of energies of conjugation and isomerization of these molecules.     

Le problème de la réduction des intégrales électroniques dans la méthode L.C.A.O. améliorée

Résumé L'auteur reprend les principes de la méthode L.C.A.O. améliorée en vue d'une justification plus complète des procédés employés. La théorie des perturbations permet d'une façon simple de tenir compte de la corrélation entre les électrons grâce à l'introduction d'une fonction universelle de la distance entre deux électrons. Le problème est ainsi ramené de l'échelle moléculaire à l'échelle atomique. On montre que la corrélation entre les électrons entraîne la réduction des intégrales atomiques. Le problème de la réduction des intégrales coulombiennes est traité en détail. La possibilité de négliger les autres intégrales biélectroniques est ensuite examiné. Enfin est étudié le problème de la réduction des intégrales de coeur.

---

The principles of the improved LCAO theory are investigated to give a better justification for its methods. Perturbation theory allows a simple account for electronic correlation, when a universal function of interelectronic distance is introduced. The problem is hereby reduced from molecular to atomic scale. The reduction of electronic energy integrals by correlation is shown, especially for Coulomb integrals. The possibility of neglecting the other bielectronic integrals is examined. Finally the problem of core integral reduction is studied.

---

Zusammenfassung Die Grundlagen der verbesserten LCAO-Methode werden untersucht, um dieses Verfahren besser zu rechtfertigen. Mit einer allgemeinen Funktion des Abstandes je zweier Elektronen und der Störungstheorie läßt sich die Elektronenkorrelation auf einfache Weise berücksichtigen. Damit wird das Problem vom molekularen auf den atomaren Maßstab zurückgeführt. Die Elektronenkorrelation bringt eine Reduktion der Elektronenenergieintegrale mit sich; die Coulombintegrale werden im einzelnen behandelt. Anschließend wird die Möglichkeit untersucht, die übrigen Zweielektronenintegrale zu vernachlässigen. Schließlich wird die Reduktion der Rumpfintegrale behandelt.

---

---

Nous tenons à remercier très vivement le Docteur Chr. K. Jørgensen (Cyanamid European Research Institut, Genève) pour les intéressants échanges de vue que nous avons eu sur les divers problèmes évoqués dans cet article ainsi que le Docteur G. Berthier (Institut de Biochimie théorique, Paris) et Monsieur H. v. Hirschhausen.     

Recherches sur la structure électronique de composés soufrés (méthode L.C.A.O. améliorée)

Improved L.C.A.O. method primitively built for conjugated molecules holding only atoms of second row in the periodic classification is extended to molecules holding atoms of the third row. The application is done for thiophen, thioketones, SO₂ and SO₃. d orbitals are not introduced in this study. Discussion about results shows that d orbitals must be introduced when the sulphur atom is strongly positively charged like in sulphur oxides.     

Halogénures Alcalins: Un Modèle Incluant une Délocalisation à Courte Distance Application à la Stabilité Relative des Divers Arrangements Cristallins

The introduction of symmetry-adapted hybrid atomic orbitals on the metallic atoms allows us to divide the crystal into elementary cells which contain 8 valence electrons each. These cells are described by linear combinations of the halogen valence shell s and p orbitals and the hybrid orbitals of the nearest metallic atoms which point to the halogen. The electronic delocalization of the halogen ions is very weak (?0.02) for: LiF, NaF, KF, LiCl, NaCI, and KCI. The cell energy in the crystal is obtained by using a first-order perturbative treatment. In agreement with experiment, the f.c.c. type is found more stable than the b.c.c. or the blende type.     

Theoretical study of the adsorption of silver atoms on the (111) face of silicon

The adsorption of one or many silver atoms on a (111) silicon face (reduced to 61 dangling atomic orbitals) is investigated by means of a self-consistent Hartree–Fock method parametrized from atomic and thermodynamical data. The valley sites (above three Si atoms) are favored over the top sites (above one Si atom). The extrapolation of the results obtained for several structures corresponding to the adsorption of n = 1, 2, 3, 4, 6, and 7 Ag atoms allows us to conclude that the most stable structures correspond: for \documentclass{article}\pagestyle{empty}\begin{document}$ \theta = \frac{1}{3} $\end{document} to linear Ag chains (3 × 1 phase), for \documentclass{article}\pagestyle{empty}\begin{document}$ \theta = \frac{2}{3} $\end{document} to an honeycomb lattice (\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt 3 \times \sqrt 3 $\end{document} phase), and for θ = 1 to a centred hexagonal lattice (\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt 3 \times \sqrt 3 $\end{document} phase), the Ag atoms located at the centers of the hexagons being beneath the plan of the hexagons. The adsorption energies corresponding to the various θ are practically equal (ca. 3 eV/Ag). The net charges of Ag atoms are equal to 0.35.     

The complete symmetrization of quantum operators: new thoughts on an old problem

The complete symmetrization with respect to x, p _x,... of the operators associated with dynamical properties can sometimes lead to results different from those obtained by the conventional quantum formalism based on the rule op (A ²)=(op A)². For example, angular momentum operators M _z ² and M ² are modified by the additive constants ²/2 and 3 ²/2 respectively (M ²0 for electron in the ground state of H atom, rotator never at rest, but spectra unchanged); the average quadratic dispersion of energy is different from zero. These results can be interpreted by assuming that the system is never strictly isolated but communicates with the other systems of the universe by means of electromagnetic interactions. Quantum mechanics would give only average values over a sufficiently long time and would exhibit a quasi-ergodic character. Examples supporting this possibility are given, in particular that of arsines for which quantum forecasts correspond to average values over one year.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday     

Recherches sur la structure électronique et les caractéristiques des différentes formes tautomères de la purine

Résumé Les caractéristiques électroniques (énergie, charges , géométrie, moment dipolaire, énergie de transition) des quatre formes tautomères de la purine et des phényl-8 N(1)H et N(3)H purines ont été déterminées par la méthode LCAO améliorée. La forme 9 est trouvée la plus stable à l'état isolé. Une interprétation nouvelle des bandes d'absorption est proposée.

---

Researches on the electronic structure and the characteristics of various tautomer forms of Purine

The electronic characteristics (energy, charge , geometry, dipole moment, transition energy) of the four tautomeric forms of the purine and of the phenyl-8 N(1)H and N(3)H purines have been determined by the improved LCAO method. The form 9 is considered as the most stable at the isolated state. A new interpretation of the absorption bands is proposed.

---

Zusammenfassung Die elektronischen Charakteristiken (Energie, Ladung , Geometrie, Dipolmoment, Übergangsenergie) der vier Tautomerformen des Purins und der Phenyl-8 N(1)H und N(3)H Purine sind durch die verbesserte LCAO-Methode bestimmt worden. Die Form 9 ist, zum isolierten Stand, als am meisten beständig zu betrachten. Eine neue Erklärung der Absorptionsbänder ist vorgeschlagen.

---

---

Les auteurs remercient le Professeur B. Pullmann (Paris) de l'intérêt qu'il a porté à ce travail, ainsi que Madame H. Feilchenfeld (Jérusalem) pour les résultats inédits qu'elle a bien voulu leur communiquer.     

A theoretical study of the difference in the behavior ofl- andd-alanine toward the two inverse forms of kaolinite

The adsorption ofl- andd-alanine on kaolinite is studied by means of the self-consistent field method, the field created by the crystal being simulated by that of 230 point charges, corresponding to two layers. The absolute structure we have adopted for kaolinite is that for whichthe ( ) trihedron is direct. Indeed, it has been shown that, owing to the nuclear weak interactions, this structure is more stable than the inverse structure. On the adopted structure, the l forms of the positive ion and of the zwitterion are more easily adsorbed than the d forms. The difference between the adsorption energies of thel andd forms are 0.14 and 0.04 kJ mol^–1 for the positive ion and the zwitterion, respectively. These differences are considerably larger than those arising from the weak interactions (ca. 10^–17 kJ mol^–1) so that the asymmetrical adsorption on kaolinite seems to be one of the causes of thel homochirality observed for the amino acids of proteins.