Electron correlations in hydrocarbon molecules

An extensive investigation is made of electron correlations in the ground state of hydrocarbon molecules. This is done by starting from a semiempirical self-consistent field (SCF) calculation. The interatomic correlations are studied by means of a previously developed local approach to the correlation problem. It is demonstrated that the various contributions to the interatomic correlation energy can be described by simple analytical expressions which depend on the type of bond as well as on the bond lengths and angles. The results are easily understood in physical terms. The intraatomic correlations are obtained from an atoms in molecules type of approach as elaborated by Lievin et al. It makes use of a population analysis of the ground-state wave function as well as of calculations for the C and H atoms. We have then a very simple, and as it turns out rather accurate calculational scheme at hand. The computational times involved are of the same order as those for the fast SCF programs. As an application of the theory we have calculated the correlation energy difference between naphthalene and azulene.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

Calculation of excited molecular states taking account of partial relaxation of the core

Effects of electron-core relaxation in the excitation of atomic systems are considered. A new approach to the consideration of relaxation is proposed, and the corresponding equations are obtained. In the -electron approximation, the first excited states of some organic molecules are calculated by the V^(N–1)-potential method, the Morokuma-Iwata method, and a method proposed in the present work.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 55–59, October, 1985.     

Use of the wittig reaction for synthesizing 2-deoxy-L-glucose

Conclusions The Wittig reaction was carried out between 2,3:4,5-diisopropylidene-al-L-arabinose and tolyloxy-methylenetriphenylphosphorane, and 2-deoxy-L-glucose was synthesized in a high yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 892–895, April, 1970.     

Comparative study of reflectance cells for PLS-FTIR determination of sugars in soft drinks

A comparative study has been carried out between a horizontal Attenuated Total Reflectance (h-ATR) cell and a Cylindrical Internal Reflection (CIR) cell (CIRCLE cell). Both cells were employed for the determination of glucose, fructose, sucrose and total sugar in soft drinks and fruit juices using absorbance measurements at two resolution values (4 and 8 cm^–1). Data were processed by Partial Least Squares regression (PLS). Using a resolution of 4 cm^–1, mean relative errors of prediction from 0.6% to 1.3% were obtained using the horizontal-ATR and from 0.6% to 2.8% using the CIRCLE cell resulting in a limit of detection from 0.03% in the case of sucrose to 0.21% for total sugar for the h-ATR and from 0.06% for sucrose to 0.13% for glucose using the CIRCLE cell. Both cells provided appropriate figures of merit, but the analytical sensitivity obtained using the h-ATR cell was three times higher than that obtained using the CIRCLE cell.     

Abnormal broadening in triplet-to-triplet absorption spectra caused by aromatic solvents

The triplet-triplet absorption spectra of a number of aromatic molecules were shown to be broadened in low temperature matrices formed by aromatic solvents (toluene, 4-isopropylbiphenyl) as compared with those in aliphatic solvents (ethanol, methylcyclohexane, triethylamine). The effect is exponentially dependent on the energy of the upper triplet state of the solute molecule. The phenomenon is discussed in terms of a strong exchange-resonance interaction between the triplet states of solute and solvent.