Semiempirical studies of core electron binding energy shifts: Part 5. SCC—MO investigation of keto—enol tautomerism in some 1,3-diketones and related anhydrides

The keto—enol tautomerism in malonaldehyde and some related 1,3-diketones is thoroughly discussed by the calculation of inner-core binding energies. The semiempirical wave-functions were obtained by the self-consistent charge (SCC—MO) molecular orbital procedure. The calculated O(1s) binding energies are generally in good agreement with available experimental data. The discrepancy found for the alcohol-type oxygen in acetylacetone is so large that it strongly indicates an error in experimental assignment. The calculations also provide conclusive evidence that enol-forms possess asymmetric hydrogen-bonded protons.     

A theoretical study of the vibronic structure in the electronic spectrum of HNO+

The results of an ab initio study of the vibronic and rotational structure in the ²Π state of HNO⁺ are presented. It is shown that the absorption spectrum at 7200 Å observed by Herzberg could be caused by the transition from the ground to the first excited electronic state of HNO⁺     

Nonlinear Parabolic Equations with Singularities in Colombeau Vector Spaces

We consider nonlinear parabolic equations with nonlinear non-Lipschitz＇s term and singular initial data like Dirac measure, its derivatives and powers. We prove existence-uniqueness theorems in Colombeau vector space yC^1,W^2,2（[0,T）,R^n）,n ≤ 3. Due to high singularity in a case of parabolic equation with nonlinear conservative term we employ the regularized derivative for the conservative term, in order to obtain the global existence-uniqueness result in Colombeau vector space yC^1,L^2（[0,T）,R^n）,n≤ 3.     

Exploratory study of insurance companies in selected post-transition countries: non-hierarchical cluster analysis

Central European Journal of Operations Research - This paper focuses on the analysis of business practice of insurance companies in selected post-transition European countries. Specifically, it...     

Stimulation of Wood Degradation by Daedaleopsis confragosa and D. tricolor

Applied Biochemistry and Biotechnology - Biological pretreatment of the lignocellulosic residues, in which white-rot fungi have a crucial role, has many advantages compared to the chemical,...     

Dynamics and stability of evolutionary optimal strategies in duopoly

Central European Journal of Operations Research - In this paper, we analyse the company behaviour in duopoly taking into account the most common strategies, including dominant, reactive,...     

Excitation of Electronic States of CO in Radio-Frequency Electric Field by Electron Impact

Electron impact excitation rate coefficients for singlet and triplet electronic states of the carbon monoxide molecule have been calculated under non-equilibrium conditions in the presence of radio-frequency electric field. A Monte Carlo simulation of electron transport has been performed in order to determine non-equilibrium electron energy distribution functions within one period of applied electric field. By using these distribution functions and corresponding cross sections, the excitation rate coefficients have been calculated for all electronic states of CO in the frequency range from 13.56 up to 500 MHz, at reduced root mean square electric field values ranging from 200 to 700 Td. We expect these rates to be valuable for modeling radio-frequency CO plasmas since excited neutrals exhibit greater chemical reactivity than neutrals in ground electronic state, hence altering many properties of plasma.     

C–H⋅<Emphasis Type="Italic">s</Emphasis>O hydrogen bond networks in <Emphasis Type="Italic">E</Emphasis>- and Z-unsaturated esters of C-glycosides

Methyl E(Z)-4,7 anhydro-5-benzamido-6,8-di-O-benzoyl-2,3,5-trideoxy-d-allo-oct-2-enoate have been synthesized like intermediates and isolated as single crystals during the synthesis of pyrazole-related C nucleosides as synthetic product with cytotoxic activity.¹ Crystal structures of E(Z) isomers were determined by X-ray analysis. E isomer crystallizes in the triclinic crystal system, space group P1, a = 5.319(1) Å, b = 10.758(2) Å, c = 12.229(2) Å, α = 72.38(2)^∘, β = 89.97(2)^∘, γ = 87.07(2)^∘, D_x = 1.320 Mgm⁻³ and Z isomer in the orthorhombic crystal system, space group P2₁2₁2₁, a = 5.1297(13) Å, b = 19.667(5) Å, c = 25.871(6) Å, D_x = 1.348 Mgm⁻³. The molecular structure was solved by direct method on the basis of 2609 and 2727 unique reflections recorded at the temperature 293 K (E-isomer) and 173 K (Z-isomer) up to the final R-factor 0.0378 and 0.0435, respectively. C–H⋅sO contact networks were analyzed and the correlation established between the existence of the weak C–H⋅sO hydrogen bonds and the melting point of the single crystals.     

Quantum chemical calculations of electronically excited states: formamide, its protonated form and alkali cation complexes as case studies

The properties of formamide, its protonated form and interaction complexes with lithium and sodium cations were studied in electronically excited singlet states by means of high-level multireference ab initio methods. The vertical excitation energies show a marked influence on protonation with particular large effects found for the O-protonated form as compared to neutral formamide. Complexation with Li⁺ and Na⁺ leads to a pronounced shift of the n_O–π^* state to higher energies while the π–π^* state moves in opposite direction. Geometry optimizations in the lowest excited singlet show strong geometrical effects leading to pyramidalization at the N and C atoms. The photodynamical simulations performed for formamide in the first excited singlet state show that the main primary deactivation path is CN dissociation with a lifetime of about 420?fs.