Efeitos de substituintes na ligação de hidrogênio do 3-hidroxipropenal

The effect of substituents on the energies and geometries of 3-hydroxypropenal was studied using the B3LYP/6-311++G(d,p) model. The hydrogen bond energies indicate that the strongest donors and the weakest acceptors present the highest and the weakest hydrogen bonds, respectively, indicating the validity of the Madsen RAHB model. Geometric parameters indicate that the intensity of the hydrogen bond is proportional to the resonance, as suggested by the RHAB model. The effect of substituents diverges from the model proposed by Gilli et al. Sometimes the results indicate that the donor or acceptor effect is more important than the point of substitution.

Um estudo teórico relativo à não-linearidade da ligação de hidrogênio em sistemas heterocíclicos C2H4O-C2H2 e C2H4S-C2H2

B3LYP/6-31G(d,p) calculations were used to determine the optimized geometries of the C2H4O-C2H2 and C2H4S-C2H2 heterocyclic hydrogen-bonded complexes. Results of structural, rotational, electronic and vibrational parameters indicate that the hydrogen bonding is non-linear due to the pi bond of the acetylene interacting with the hydrogen atoms of the methyl groups of the three-membered rings. Moreover, the theoretical investigation showed that the non-linearity is much more intriguing, since there is a structural disjunction on the acetylene within the heterocyclic system.

SAPT: ligação de hidrogênio ou interação de van der Waals?

It is through the application of an electronic partition approach called Symmetry-Adapted Perturbation Theory (SAPT) that the nature of hydrogen bonds and van der Waals interactions can be unveiled according to the contribution of electrostatic, charge transfer, exchange repulsion, polarization, and dispersion terms. Among these, electrostatic partition governs the formation of the hydrogen bonds, whose energies are arguably high. However, the weakness of the interaction strength is caused by dispersion forces, whose contribution decisively lead to the stabilization of complexes formed via van der Waals interactions.

A regra de Bent contextualiza a força da ligação de hidrogênio em clusters trimoleculares

This article presents a theoretical study of the molecular properties of trimolecular clusters of CnHm∙∙∙HCN∙∙∙HX formed by the ϖ∙∙∙H and n∙∙∙H hydrogen bonds. The interaction strengths of these interactions are in line with the variations in s-character, and independently, the red-shift rise whether stronger or weaker bound systems are carried out. This behavior was justified via NBO analysis and supported by Bent´s rule, wherein the greater variations in s-character of X are in good agreement with larger red-shifts and vice-versa. To conclude, the refinement of the supermolecule approach and NBO binding energies also corroborate in this regard.

A INFLUÊNCIA DA LIGAÇÃO DE HIDROGÊNIO EM REAÇÕES QUÍMICAS: REAÇÃO DE PRILESCHAJEW

Theoretical analysis at the BHandHLYP/6-311++G(d,p) level of theory with the support of QTAIM calculations was used to reinvestigate the structure of an intermolecular system formed between ethylene oxide (C2H4O) and formic acid (HCO2H) after the epoxidation known as the Prileschajew reaction. Geometric and infrared vibration results revealed that HO2CH forms a strong hydrogen bond with C2H4O followed by a larger red-shift of the H−O bond. NBO analysis was applied to justify this frequency shift. Finally, QTAIM calculations identified the formation of two hydrogen bonds, namely O···H−O and H···O=C.

O ESTADO DA ARTE DA LIGAÇÃO DE HIDROGÊNIO

Along the historical background of science, the hydrogen bond became widely known as the universal interaction, thus playing a key role in many molecular processes. Through the available theoretical approaches, many of these processes can be unveiled on the basis of the molecular parameters of the subject intermolecular system, such as the variation of bond length and mainly the frequency shift observed in the proton donor. Supported by the natural bond analysis (NBO) with the quantification of the hybridization contributions, the structural deformations and vibrational effects cited above are also attributed to the outcome of the intermolecular interaction strength, which consequently can be estimated by means of the quantum theory of atoms in molecules (QTAIM) as well as evaluated by the symmetry-adapted perturbation theory (SAPT). Moreover, to identify the preferential interaction sites for proton donors and acceptors, the molecular electrostatic potential (MEP) is useful in this regard.

Compostos heterometálicos. Interação do tricarbonil com ligação W-Hg, [WCl(CO)3(bipy)(HgCl)], com tiouréias

Foram efetuadas reações entre o heterometálico [WCl(CO)3(bipy)(HgCl)], (bipy = 2,2'-bipiridina) e tiouréias que levaram à formação de compostos do tipo [WCl(CO)3(bipy)(HgCl)L] [L = tiouréia (tu); N-metiltiouréia (mtu); N,N-dimetiltiouréia (dmtu)]. Os espectros de absorção no infravermelho mostram que a esfera de coordenação do tungstênio mantêm-se inalterada e que as tiouréias encontram-se ligadas ao átomo de mercúrio através do átomo de enxofre.

Avaliação de linhas de beneficiamento e impactos de queda na qualidade de caqui "Rama Forte"

O manuseio inadequado e excessivo de frutas e de hortaliças causa alta incidência de danos físicos e, consequentemente, perdas pós-colheita. O objetivo deste trabalho foi avaliar a magnitude de impacto em linhas de beneficiamento e classificação para caqui "Rama Forte" e determinar, em laboratório, seus limites de impactos. Para a avaliação dos pontos críticos, foi utilizada uma esfera instrumentada de 76 mm de diâmetro (Techmark, Inc., Lansing, EUA), que registrou a magnitude dos impactos em sete equipamentos distintos de quatro unidades de beneficiamento. A determinação de danos físicos foi feita em testes laboratoriais, nos quais a queda dos frutos foi relacionada com a magnitude de impacto, incidência de danos físicos e perdas na qualidade do fruto. Nas linhas de beneficiamento, os valores de impactos encontrados variaram de 21 a 87 G nos pontos de transferência, e a maioria dos impactos registrados (acima de 94%) durante a passagem pela linha foram de valores de até 50 G. Alturas de queda a partir de 20 cm causaram aumento na perda de massa do caqui no sexto dia de armazenamento, em temperatura ambiente. As quedas de 20 e 30 cm causaram maior escurecimento da casca (menores valores de L), associada à redução da intensidade da cor (chroma). O impacto não causou efeito nas características químicas da polpa do fruto.

Quatre quatuors pour le clavecin ou piano forte accompagnés d'une flute, violon et violoncelle : Oeuvre premiere

Soitinnus: huilu, viulu, sello, cembalo tai piano.

Six sonates pour le clavecin ou le piano forte avec l'accompagnement d'un violon ou flute : Oeuvre sixième

Soitinnus: viulu/huilu, cembalo/piano.

Trois sonates pour le clavecin ou piano forte, accompagnés d'une flute & violoncel : Oeuvre XVII. Libro I

Soitinnus: huilu, sello, cembalo/piano.

Six nouveaux walses pour le forte-piano avec accomp: de violon ou flute ad lib

Soitinnus: viulu/huilu, piano.

Gothebourg : ville forte port de mer sur l'océan de la province de Westro-Gotland au nord du destroit appellé l[a] Sond, située sur la rivière d[e] Trollhette

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan