Vol 59, No 4 (2016)

Based on an analysis of experimental and theoretical works, modern notion on conditions of forming of population density inversion on self-terminating IR transitions of alkali-earth metals is given. It is demonstrated that there is a significant difference in the inversion formation in lasers on self-terminating transitions in the visible and near-IR ranges and lasers on self-terminating transitions of alkali-earth metals lasing IR lines in the mid-IR range. It is shown that in the discharge circuit of lasers on self-terminating metal atom transitions (LSMT) there are processes strengthening the influence of the known mechanism limiting the frequency and energy characteristics (FEC) of radiation caused by the presence of prepulse electron concentration. The mechanism of influence of these processes on FEC of the LSMT and technical methods of their neutralization are considered. The possibility of obtaining average lasing power of ~200 W from one liter volume of the active medium of the strontium vapor laser is demonstrated under conditions of neutralization of these processes.

The paper presents brief information about the establishment and development in Tomsk of high-resolution molecular spectroscopy – the field of science closely related to a study of the optical properties of the atmosphere. The methods and the current state of high-resolution laser spectroscopy and Fourier spectroscopy are described together with new results of mass measurements. The developed theoretical methods for a study of molecular spectra, including methods of their global analysis and information systems of spectral databases, are presented.

Models of quantum-chemical calculation of rate constants for internal processes and intersystem crossing in polyatomic molecules are considered. The influence of the nature of electronically excited states in organic compounds is investigated. It is shown that the explicit allowance for the nature of wave functions of electronic states for estimation of electronic matrix elements of nonadiabaticity operators and spin-orbit interaction allows photophysical processes in organic compounds to be considered in detail.

A study of electronic states of LiO, NaO, KO, MgO, and CaO molecules has been performed. Potential energy curves of the investigated molecules have been constructed within the framework of the XMC-QDPT2 method. Lifetimes and efficiencies of photolysis mechanisms of these monoxides have been estimated within the framework of an analytical model of photolysis. The results obtained show that oxides of the considered elements in the exospheres of the Moon and Mercury are destroyed by solar photons during the first ballistic flight.

The influence of H₂O₂ on the photodegradataion of 5-methoxypsoralen (5-MOP) in ethanol and in waterethanol solutions upon exposure to KrCl excilamp radiation (λ_rad = 222 nm) and XeBr excilamp radiation (λ_rad = 283 nm) is investigated. A kinematic model of photodegradation of the investigated molecule is constructed. The addition of H₂O₂ resulted in a weak increase of the decay rate of 5-MOP in ethanol exposed to KrCl excilamp radiation. In water-ethanol solutions the addition of H₂O₂ altered the mechanism of decay of 5-MOP irradiated by the KrCl excilamp in comparison with irradiation by the XeBr excilamp. It has been shown that upon exposure to XeBr excilamp radiation in the presence of H₂O₂, the primary photoproduct of the transformation of 5-MOP in the reaction corresponding to the first-order kinetic model is formed both in ethanol and in the water-ethanol solutions. Maximum removal of 5-MOP takes place for the ratio of initial concentrations [5-MOP]:[H₂O₂] = 1:3 after 60 min irradiation. It is found that irradiation by the XeBr excilamp the decay rate of 5-MOP is 5 times higher in the water-ethanol solutions in comparison with ethanol. Upon exposure to KrCl excilamp radiation the mechanism of 5-MOP decay corresponds to a pseudo-firstorder kinetic model. The nature of the dependence of the decay rate of 5-MOP on the irradiation time for the ratio of initial concentrations [5-MOP]:[H₂O₂] = 1:24 indicates that during decay of the initial compound a photoproduct appears in the system which decays during the irradiation time into secondary compounds. Efficient removal of 5-MOP under this irradiation takes place for the ratio of initial concentrations [5-MOP]:[H₂O₂] = 1:10 after 60 min irradiation.

Optical properties of some boron dipyrromethene difluoro (III) (BF2-dipyrromethene) derivatives are studied depending on the ligand structure, the medium in which they are incorporated, irradiation time, and radiation wavelength. Prospects for application of the prepared solid-state media painted by the examined compounds in various optical devices used in modern technologies are demonstrated. These are active laser media in the range 550–565 nm based on three-component silicate matrices with high laser damage threshold and sensor media based on boron difluoride complexes of halogen-substituted dipyrromethenes incorporated into an organic polymer for the determination of oxygen concentration in a gas mixture. Spectral, energy, and resource characteristics of lasing of solid-state elements are presented. The effect of reversible dye photounpainting in three-component silicate matrices with subsequent restoration in the darkness is discovered. Possible reasons for this effect are discussed with allowance for which laser media with increased photostability can be prepared. A high sensitivity of the sensor medium based on diiodinated complex of BF2-dipyrromethene incorporated into polyvinyl butyral is obtained. Reasons for the increase in the response time to the change of the gas mixture when going over to neutral argon and possibilities of its elimination are discussed.

The spectral properties of two substituted divinyl dibenzothiophene sulfone in solutions of tetrahydrofuran, polyvinylcarbazole films, and films obtained by thermal vacuum deposition are investigated. The ability of these compounds in thin-layer ITO/PEDOT:PSS/NPD/L/Ca/Al and ITO/PEDOT:PSS/PVK+L/Ca/Al structures (L denotes the examined luminophore) to emit radiation at applied voltage is investigated. It is shown that the spectra of photo- and electroluminescence in the film have a strong red shift of ~100 nm compared to the photoluminescence in solutions. It is suggested that radiation belongs to excimers.

Interaction of humic acids with polyaromatic hydrocarbons (PAH) (naphthalene and anthracene) and triazole series fungicides (cyproconazole (CC) and tebuconazole (TC)) is investigated by the method of fluorescence quenching depending on the concentration of substances in solutions and their structural features. Humic acids were modified by mechanochemical activation in a planetary mill. The complex character of intermolecular interactions between PAH and fungicides with humic acids, including donor-acceptor and hydrophobic binding, is established. Thermodynamically stable conformations of biocide molecules were estimated using ChemOffice CS Chem3D 8.0 by methods of molecular mechanics (MM2) and molecular dynamics. Biocide molecules with pH 7 are in energetically favorable position when the benzene and triazole rings are almost parallel to each other. After acidification of solutions to pH 4.5, the CC molecule retains the geometry for which donor-acceptor interactions are possible: the benzene ring in the molecule represents the electron donor, and triazole is the acceptor. In this case, the electron density in CC is redistributed easier, which is explained by a smaller number of carbon atoms between the triazole and benzene rings, unlike TC. As a result, the TC triazole ring is protonated to a greater degree, acquiring a positive charge, and enters into donoracceptor interactions with humic acid (HA) samples. The above-indicated bond types allow HA to participate actively in sorption processes and to provide their interaction with biocides and PAH and hence, to act as detoxifying agents for recultivation of the polluted environment.