Nonradiative deactivation of the lowest triplet state of naphthalene and its hydroxy derivatives at 77 K

The validity of an inductive resonance theory of energy transfer from the T ₁→S ₀ transition dipole to overtone vibrations of molecular groups containing H and D atoms is experimentally tested for a series of compounds whose conjugation systems are similar in size. To this end, by using kinetic, spectral, and luminescent methods (measurements of the phosphorescence decay times, phosphorescence spectra, ratios between the quantum yields of phosphorescence and fluorescence at 77 K, total quantum yields of fluorescence at 293 K, and ratios between the quantum yields of fluorescence at 293 and 77 K), the deactivation processes of the lowest excited T ₁ and S ₁ states of seven emitting centers (naphthalene, its hydroxy and dihydroxy derivatives, and their monoanions) in solutions in ethanol-h ₆, ethanol-d ₆, and their 2: 1 mixtures with diethyl ether are studied. For all the compounds studied, the rate constants k _r of the radiative T ₁→S ₀ transition and the changes in the overlap integrals of the spectra of phosphorescence and absorption of overtones of CH stretching vibrations are determined. The rate constants of energy transfer k _dd(CH) from the T ₁→S ₀ transition dipole to the stretching vibrations of the CH bonds are calculated without regard for the changes in the localization and orientation of this transition dipole in the compounds under study. The contribution of an individual CH group k _nr(CH) to the total rate constant of nonradiative deactivation of the T ₁ state averaged over the CH groups of the naphthalene ring system is ascertained. A good correlation between the changes in the constants k _nr(CH) and k _dd(CH) in the series of the hydroxy derivatives of naphthalene is found, which is indicative of the inductive resonance mechanism of the energy degradation of the T ₁ state. The deviations from proportionality between the changes in these constants upon passing from naphthalene to its hydroxy derivatives, which correlate with a marked increase in the radiative constant k _nr of the hydroxy derivatives in comparison with naphthalene, indicate changes in the strength and localization of the T ₁→S ₀ transition dipole moment and in its orientation with respect to the plane of the molecule that occur due to introduction of a heteroatom, oxygen, whose lone pair of electrons enters into conjugation with the πelectrons of the naphthalene ring system.     

Intramolecular interactions and deuteration effect in nonradiative deactivation of lowest triplet state of anthracene and naphthalene

In the approximation of nonadiabatic interactions and considering all out-of-plane vibrational modes to be promoting ones, we calculate changes in the rate constants T _s K _dg ^s of the nonradiative degradation T ₁ ^s ⇝ S ₀ of in-plane spin (s) triplet states as a result of the complete deuteration of anthracene and naphthalene molecules. We examine how the deuteration, the frequency factor, and the shape of promoting vibrational modes affect the squared matrix elements of both nonadiabatic coupling and adiabatic vibronically induced spin-orbit (VISO) coupling of electronic states. The compensation effect of spin-orbit interactions in structural elements of the carbon backbone of the anthracene molecule is ascertained.     

The role played by some factors of intramolecular interaction in nonradiative deactivation of the lowest triplet state of octachlorodibenzo-p-dioxin

We have studied how intramolecular interactions, such as vibronically induced spin-orbit (VISO) and nonadiabatic interactions, which are governed by different structural elements of the octachlorodibenzo-p-dioxin (OCDD) molecule, affect the deactivation of its lowest triplet state. In the nonadiabatic approximation, taking into account out-of-plane vibrational modes as promoting ones, we have estimated the values of rate constant K _dg ^s of the nonradiative energy deactivation of in-plane triplet sublevels (s = z, y) of the triplet state of the OCDD molecule.     

The spin-lattice relaxation mechanism in the phosphorescent triplet state

A new mechanism is proposed for spin-lattice relaxation (SPL) in the phosphorescent triplet state of a molecule that has no inversion point. The mechanism is based on the fact that the internal spin-orbital interaction in a molecule allows the transition between spin sublevels of the triplet induced by the variable crystal field of the lattice.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 27–31, May, 1978.     

On the concentration dependence of the sensitized phosphorescence quantum yield of naphthalene in toluene at 77 K

A concentration dependence of the sensitized phosphorescence quantum yield of naphthalene (with benzophenone as a donor) in equimolar toluene solutions at 77 K is studied for concentrations of components ranging from 0.1 to 0.5 mole/litre. A nonmonotonic character of this dependence is established. With increasing solution concentration, intervals of increase (from 0.1 to 0.35) and decrease (from 0.35 to 0.5) of the sensitized phosphorescence quantum yield are observed. Reasons for this dependence are discussed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 3–6, October, 2004.     

The methyl group rotation barrier of dimethylacetylene in the solid state at 4.5 K

The librational ground state splitting of the methyl groups in solid dimethylacetylene has been measured by high reso resolution neutron scattering at 4.5 K. A threefold rotational barrier of 45 ± 5 meV (=1.04 kcal/mole) has been obtained.     

Excited state charge-transfer effect on the phosphorescence emissions of 4-aminopyridine at 77 K

Absorption and phosphorescence spectral characteristics of 4-aminopyridine (AMP) have been studied in polar and non-polar solvents at 77 K. Absorption data provide evidence that the excited singlet π,π¹ states of the molecule possess substantial charge-transfer (CT) character. The 4-AMP molecule is nonfluorescent in all the solvents used in the investigation but phosphoresces strongly in ethanol glass at 77 K. The phosphorescence emissions have a lifetime and negative polarization characteristic of π,π¹ origin. From the observations that in acidic ethanol glassy medium the phosphorescence quantum yield somewhat decreases and the lifetime moderately increases as compared to that in neutral ethanol glass but the negative polarization persists, it has been concluded that all the coupling schemes ¹π,π¹(CT)^$\text{SO3}$π,π¹, ¹π,π^{1$\text{SO3}$}n,π^{1$\text{vib3}$}π,π¹ and ¹π,π^{1$\text{vib1}$}n,π^{1$\text{SO3}$}π,π¹ are responsible for the phosporescence characteristics of 4-AMP molecule. The substatial reductionsin the values of the phosphorescence quantum yield and lifetime of 4-AMP in non-polar rigid matrix at 77 K have been attributed to enhanced nonradiative process arising from increased vibronic interactions between the closely spaced ³n,π¹ and ³π,π¹ states of the molecule in such environment.     

Isothermal bulk modulus of solid xenon for zero pressure at 4.2 K, 65 K and 77 K

An interferometric method has been used to measure the isothermal bulk modulus (the reciprocal of the compressibility) of solid xenon at zero pressure for several temperatures. It is the first time that an elastic constant of this substance has been measured at a temperature below 10 K. The smoothed results are (37.9 ± 0.5) kbars at 4.2 K, (29.6 ± 0.5) kbars at 65.6 K, and (28.2 ± 0.5) kbars at 77 K.     

Photoinduced energy transfer from the triplet state of naphthalene moiety in the Tb/Eu complexes of a specially designed naphthalene cryptand

The paper reports time-resolved emission and energy transfer (ET) studies of metal ion complexes of a specially designed rigid macrocyclic naphthalene cryptand (L) under different conditions. Complex formation of L with Li⁺ and H⁺ causes an appreciable increase in singlet state quantum yield and lifetime of L implying photoinduced electron transfer (PET) from the cryptand moiety to naphthalene unit in the free L. The system exhibits photoinduced ET at 77 K in its Tb³⁺ and Eu³⁺ complexes with either NO₃⁻¹ or Cl⁻¹ as counter-anion. The extent of ET is higher for the Tb³⁺ complex as compared to that for the Eu³⁺ complex. In both Tb³⁺ and Eu³⁺ complex, the NO₃⁻¹ ions influence the relative orientation of donor (L) and acceptor (Ln³⁺) more in favour of ET than the Cl⁻¹ ions. The rate constants for the ET from the naphthalene moiety of L to the acceptor (Ln³⁺) have been evaluated at 77 K. The results suggest ET from the triplet state of naphthalene using an exchange mechanism. The ground state geometries of the system L and its complexes with Li⁺, Cs⁺ and Tb³⁺ have been determined using DFT methods to interpret our results.     

Polarization of phosphorescence transitions and probabilities of intramolecular nonradiative deactivation of the lowest triplet state of aromatic molecules

This study continues the experimental testing of the validity of the inductive resonance theory of dipole-dipole energy transfer from the T ₁→S ₀ transition dipole to stretching vibrations of intramolecular CH bonds of naphthalene and its hydroxy derivatives. To this end, in the series of compounds under study, the range of variation of the geometrical parameter [Φ(CH)]² of the Förster theory, which accounts for the mutual orientation of the energy donor and acceptor, is estimated. Preliminarily, the angles between the transition dipole moments of the radiative and absorptive electronic transitions (T ₁→S ₀ and S ₀→S ₁; T ₁→S ₀ and S ₀→S ₂; S ₁→S ₀ and S ₀ →S ₁; and S ₁→S ₀ and S ₀→S ₂) are measured at 77 K by the method of polarization photoselection. From the polarization measurements, the angles between the phosphorescence transition dipole moment and the plane of a molecule are determined. It was found that, upon passage from naphthalene to its β derivatives, the orientation of the dipole moment of the radiative T ₁→S ₀ transition relative to the plane of a molecule markedly changes, with the in-plane component of the dipole moment being increased by an order of magnitude. The experimentally determined rate constants of nonradiative deactivation of the T ₁ state averaged over the CH groups of the naphthalene ring system, k _nr(CH), are compared with the rate constants [Φ(CH)]² of the inductive resonance energy transfer from the dipole of the T ₁→S ₀ transition to the dipole of the CH vibrations polarized in the plane of a molecule, calculated with regard to the orientational factor [Φ(CH)]². This comparison showed that, in the series of compounds under study, a change in the orientation of the dipole moment of the radiative T ₁→S ₀ transition relative to the plane of a molecule does not affect the rate of the nonradiative T ₁?S ₀ transition. This inference is confirmed by the absence of a correlation between the rate constants k _dd(CH) calculated by us (with regard to [Φ(CH)]²) and the well-known rate constants k _nr(CH) of individual sublevels of the T ₁ state measured at T≤1.35 K for a number of organic molecules. The possible sources of discrepancy between the experimental data that k _nr(CH) is independent of [Φ(CH)]² and the predictions of the theory are considered. A conclusion is made that the electronic-vibrational energy transfer between electric dipoles is the most probable mechanism of the T ₁?S ₀ transitions, but the rate constant of the dipole-dipole energy transfer upon interaction of the electronic and vibrational dipoles in a molecule does not depend on their orientations.     

The adsorption of argon on ZnO at 77 K

We have studied the adsorption of argon onto ZnO surfaces at 77 K by means of quasi-equilibrium adsorption volumetry coupled with high resolution microcalorimetry and Grand Canonical Monte-Carlo (GCMC) simulations. The adsorbate/surface adsorption potential function (PN type) used in the simulations, was determined on the basis of ab initio calculations (corrected for dispersion interactions). The first aspect of this work was to test the ability of a standard solid-state Hartree—Fock technique coupled with a perturbative semi-empirical approach in deriving a reliable adsorption potential function. The dispersion part of the adsorbate/surface interatomic potential was derived by using perturbation theory-based equations while the repulsive and induction interactions were derived from periodic Hartree—Fock (CRYSTAL92) calculations. GCMC simulations based on this adsorption potential allow one to calculate adsorption isotherms and isosteric heat versus loading curves as well as singlet distribution functions at 77 K for each type of ZnO (neutral and polar) faces. The combined analysis of the simulation data for all surfaces gives a good insight of the adsorption mechanism of argon onto ZnO surfaces at 77 K in agreement with experiment. As far as neutral surfaces are concerned, it is shown that adsorption first takes place within the ‘troughs’ which cover ZnO neutral surfaces. At low chemical potentials, these semi-channels are preferential adsorption sites in which we could detect a nearly one-dimensional adsorbate freezing in a commensurate phase at 77 K. The polar O faces are the most favourable surfaces for adsorption at higher chemical potentials.     

The relaxation peak in the internal friction of kbr and KBr-KCl solid solutions

It is considered that this peak is due to rapidly changing fluctuations in the distribution of bends in dislocation lines. The internal friction is found to vary for a time after plastic deformation or X-irradiation.I am indebted to Professor E. K. Zavadovskaya for direction in this work and to Professor A. A. Vorob'ev for discussion of the results.     

Fluorescence and absorption spectra of 9, 10-diazaphenanthrene solutions at 77°K

The S₁(n, √^*) ? S₀ fluorescence and absorption spectra of 9, 10-diazaphenanthrene solutions in hydrocarbons possess at 77°K a quasilinear structure (Shpolskii effect). In the frozen n-hexane matrix (c = 10^-4 M) the fluorescence spectrum displays a triplet structure (22 181, 22 169 and 22 149 cm^-1 for the O-O transition). The spectra of 9, 10-diazaphenanthrene solution are shifted towards the red compared with those of the single crystal (～ 900 cm^-1). A good agreement between the calculated and experimental values of this shift is obtained. A strong concentration effect on the structure of the spectra is discussed. A quasilinear structure is observed also in the second absorption band.