V. A. Tolkachev

Collisional depolarization of fluorescence of polyatomic molecules in the gas phase by excited state quenchers

A new method of extracting information on the efficiencies of quenching of an excited state and collisional reorientation from the data on the fluorescence depolarization of molecular vapors by quenchers of the excited state is proposed. The method does not involve collisional cross sections and fluorescence lifetimes. From the experimental data on the depolarization of polarized luminescence of para-quaterphenyl and 2-(4′-dimethylamine) phenyl-5-phenyloxydiazole by oxygen and nitrogen, the ratios of the constants of the excitedstate quenching and orientation randomization (fluorescence depolarization) by oxygen are obtained. For these molecules, the probabilities of the excited-state quenching q and orientation randomization s per collision with oxygen molecules are determined (q=0.25±0.04 and s=0.13±0.04 for para-quaterphenyl and q=0.2±0.04 and s=0.21±0.04 for 2-(4′-dimethylamine)phenyl-5-phenyloxydiazole). The self-quenching of fluorescence of perylene vapors, with the probability 0.28 per collision, is found.

Role of Light Polarization in the Optothermal Effect

It is shown that the highest optothermal effect in low-intensity irradiation is attained on chromophores of stationary orientation exposed to irradiation by a linearly polarized light. For chromophores with stochastization of orientation between the events of light absorption, the magnitude of the optothermal effect is independent of polarization and is three times lower than in stationary orientation. In anisotropic media, an optimally oriented linearly polarized light is more efficient.

Spectral and luminescent properties of jet-cooled dinaphthofuran

The fluorescence and fluorescence excitation spectra of jet-cooled dinaphtho[2,1-b:1′,2′-d]furan (dinaphthofuran) molecules, as well as their complexation with inert gases Ar, Kr, and Xe, are studied. The indicatrices of the degree of polarization of fluorescence of dinaphthofuran molecules upon excitation of the electronic transitions S0−S1 and S0−S2 are calculated as functions of the intramolecular orientation of the transition dipole moments. The fluorescence polarization spectrum is measured under excitation within the rotational contour of the line of the purely electronic transition v00 = 29 294 cm−1. In contrast to complex planar molecules, the S0−S2 fluorescence excitation spectrum of dinaphthofuran is found to be continuous, with the Q branch of the rotational contour being absent. The fluorescence excitation spectra of van der Waals complexes of dinaphthofuran with inert gases exhibit multiplet lines, which is associated with the helical structure of the molecules studied.

Lability of the Configuration of Free Complex Molecules and Polarized Luminescence

We compare the sensitivity of the degree of polarization of integral fluorescence for excitation by light with a spectral width larger than the width of the rotating loop or only in the Q‐branch of the rotating loop to a change in the principal moment of inertia (rotational constants) of complex molecules in vapors. It is shown that the sensitivity depends on the degree of asymmetry of the molecular top and the intramolecular orientation of the dipole transition moments. Improvement of the symmetry of the asymmetric top leads to an increase in the sensitivity to at least one of the rotational constants. Such effects are also noted for the sensitivity of the period of the rotational quantum echo to a change in the rotational constants.

Polarized Fluorescence of Jet‐Cooled Indole

The polarization of indole fluorescence on excitation in the P, Q, and R branches of a purely electron transition has been investigated. Relations are given to calculate the fluorescence polarization with arbitrary orientation of the dipole moments of transitions with absorption and emission and with excitation in the Q branch of the vibronic line. The coincidence of the measured (7.3%) and calculated (7.7%) values of the polarization degree confirms the reported intramolecular orientation of the dipole moment of transition. The measured fluorescence polarization degree on nonselective excitation is about 3%.

Polarization of the Fluorescence Excited in the P- and R Branches of the Vibronic Lines of Jet-Cooled Complex Molecules

A model is suggested to calculate the degree of polarization of the fluorescence of jet-cooled polyatomic molecules excited within the P- and R branches of the rotational contour of the vibronic line by light not providing resolution of the rotational structure. These dependences are calculated and compared with experimental data for molecules belonging to different types of asymmetric tops with different intramolecular orientation of the fluorescence transition dipole moment: anthracene; anthracene + Ar; 1,4-diaminoanthraquinone; indole; tetracene, and triphendioxazine.

Circularly Polarized Luminescence of Free Complex Molecules in a Constant Magnetic Field

It is shown that the magnetic field‐induced optical activity in the luminescence of complex molecules in vapors in the presence of rotational anisotropy in the ensemble of luminescent molecules provides information also on the intramolecular orientation of the initiating dipole moments of transitions, including borrowed ones. The relationships between the rotational force of the optical activity and this orientation in the case of anisotropy induced by a linearly polarized exciting light are obtained.