CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.     

The role of guaiacyl moiety in free radical scavenging by 3,5-dihydroxy-4-methoxybenzyl alcohol: thermodynamics of 3H+/3e− mechanisms

ABSTRACT

Participation of guaiacyl moiety of 3,5-dihydroxy-4-methoxybenzyl alcohol (DHMBA) in inactivation of free radicals was investigated using the DFT method. The thermodynamics of triple (3H⁺/3e^?) free radical scavenging mechanisms was investigated. The Gibbs free energies of reactions of inactivation of selected 10 free radicals indicate DHMBA as a potent scavenger. Obtained results allow us to suggest that the contribution of guaiacyl moiety to antioxidant activity of phenolic compounds should be taken into account, what has been scarcely considered until now.     

Selectiveness of laser processing due to energy coupling localization: case of thin film solar cell scribing

Selectiveness of the laser processing is the top-most important for applications of the processing technology in thin-film electronics, including photovoltaics. Coupling of laser energy in multilayered thin-film structures, depending on photo-physical properties of the layers and laser wavelength was investigated experimentally and theoretically. Energy coupling within thin films highly depends on the film structure. The finite element and two-temperature models were applied to simulate the energy and temperature distributions inside the stack of different layers of a thin-film solar cell during a picosecond laser irradiation. Reaction of the films to the laser irradiation was conditioned by optical properties of the layers at the wavelength of laser radiation. Simulation results are consistent with the experimental data achieved in laser scribing of copper-indium-gallium diselenide (CIGS) solar cells on a flexible polymer substrate using picosecond-pulsed lasers. Selection of the right laser wavelength (1064 nm or 1572 nm) enabled keeping the energy coupling in a well-defined volume at the interlayer interface. High absorption at inner interface of the layers triggered localized temperature increase. Transient stress caused by the rapid temperature rise facilitating peeling of the films rather than evaporation. Ultra-short pulses ensured high energy input rate into absorbing material permitting peeling of the layers with no influence on the remaining material.     

The Law of the Iterated Logarithm for Extreme Waiting Time in Multiphase Queueing Systems

The objective of this research in the queueing theory is the law of the iterated logarithm (LIL) under the conditions of heavy traffic in multiphase queueing systems (MQS). In this paper, the LIL is proved for the extreme values of some important probabilistic characteristics of the MQS, namely, maxima and minima of the summary waiting time of a customer, and maxima and minima of the waiting time of a customer.     

Mössbauer and Nuclear orientation study of magnetic atom behaviour in AuFe below the percolation threshold

An⁵⁷Fe Mössbauer study and⁶⁰Co and⁵⁴Mn nuclear orientation (NO) studies of the Au₈₆Fe₁₄ alloy have been performed. A transition to the spin glass state was observed below approximately 50 K. NO of the⁶⁰Co impurity showed absence of the polarization of the⁶⁰Co nuclei. For⁵⁴Mn impurities the dependence of the Mn effective magnetic field on external field andtemperature was found.     

2,2-Dimethylpenta-3,4-dienal derivatives: Preparation,NMR spectra,and crystal structure

Summary The preparation of some new 2,2-dimethylpenta-3,4-dienal derivatives starting byClaisen-Cope rearrangement of the pyrolytic product of the corresponding acetales and followed by condensation reactions is described. The synthesis of homoallenylketone5 from homoallenylaldehyde3 byGrignard reaction and followed by the oxidation of the formed alcohol using potassium chlorochromate (KCC) is reported. All new compounds are characterized by IR, MS,¹H, and¹³C NMR spectroscopy. The full assignment of the NMR signals is based on HETCOR and FLOCK pulse sequences. The molecular and crystal structure of 2,2-dimethylhexa-3,4-dienal 2,4-dinitrophenylhydrazone is presented.Dedicated to ProfessorFritz Sauter on the occasion of his 65th birthday     

Limit distributions of sums of random variables defined on a finite homogeneous Markov chain. I

Vilnius University, Naugarduko str. 24, 2006 Vilnius, Lithuania. Translated from Lietuvos Matematikos Rinkinys, Vol. 33, No. 4, pp. 424–434, October–December, 1993.     

On Statistical Properties of the Lerch Zeta-Function. II

A discrete limit theorem for the Lerch zeta-function with an integer parameter in the space of meromorphic functions is proved.