Spectral manifestations of <Emphasis Type="Italic">d</Emphasis>-π exchange and charge transfer interactions in Cu(II) porphyrins

New absorption bands due to spin-forbidden transitions from the ground state to excited triplet states are found at 295 K in the near-IR absorption spectra of a number of Cu(II) complexes of octaethylporphyrin (OEP) that differ in the nature, number, and position of their side substituents. The frequency distribution, number, and nature of these transitions are analyzed using computer decomposition of complex contours into Gaussian components and additional data from the phosphorescence and phosphorescence excitation spectra (295-77 K). The d-π exchange integrals, determining the energy splitting ΔE = E(²T₁)–E(⁴T₁) in the compounds under study, are calculated on the basis of the experimental data obtained. It is shown that, in addition to the formally spin-allowed ²S₀ → ²T₁ transition (λ_max = 833 nm), the absorption spectrum of the nonplanar CuOETPP molecule at 295 K exhibits the low-intensity spin-forbidden ²S₀ → ⁴T₁ transition (λ_max = 937 nm). For this compound at 77 K, phosphorescence from the ⁴T₁ state is observed (λ_max = 955 nm), with a quantum yield equal to ?_Ph = 0.0015 and a decay time amounting to τ_Ph = 190 ns. For the CuOEP-Ph(o-NO₂) molecule, which contains the electron-acceptor nitro group, direct absorption from the ground state S₀ to a charge transfer (CT) state (λ_max = 845 nm) is observed at 295 K. The extinction coefficient of this absorption and the energy of the CT state are determined.     

Observation of the distorted form of Pd-porphin in single site spectra at low temperatures

Highly resolved phosphorescence and excitation of phosphorescence spectra for palladium porphin (PdP) in polycrystalline Shpol'skii matrices at liquid helium temperatures were recorded. Two non-interactive forms of PdP in the ground state have been identified. The energy splitting between the two forms amount up to 78 cm⁻¹ for PdP in an n-octane at 4.2 K. The short-wavelength spectral form is attributed to the structure, where the central Pd(II) ion is in plane of the porphyrin macrocycle, while the long-wavelength form is associated with the nonplanar saddle-type conformation of the PdP. The frequencies of the normal vibrations in the ground electronic state have been measured separately for both forms and the differences in the normal modes of two macrocycle conformations are discussed. The set of temperature activated bands in phosphorescence spectra were found. Analysis of phosphorescence spectra at elevated temperatures and excitation of phosphorescence spectra under direct excitation in the S₀→T₁ channel make possible the value of zero-field splitting of quasi-degenerate T_1,2 state for two forms to be determined. The splitting value in n-octane matrix amount to 40 and 57 cm⁻¹ for planar and nonplanar conformations of PdP, respectively.     

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.     

Cluster decay of <Superscript>112−122</Superscript>Ba isotopes from ground state and as an excited compound system

The decay properties of various even–even isotopes of barium in the range 112 ≤A ≤ 122 is studied by modifying the Coulomb and proximity potential model for both the ground and excited state decays, using recent mass tables. Most of the values predicted for ground state decays are within the experimental limit for measurements (T_1/2 < 10³⁰ s). The minimum T_1/2 value refers to doubly magic or nearly doubly magic Sn (Z= 50) as the daughter nuclei. A comparison of log ₁₀(T_1/2) value reveals that the exotic cluster decay process slows down due to the presence of excess neutrons in the parent nuclei. The half-lives are also computed using the Universal formula for cluster decay (UNIV) of Poenaru et al and the Universal decay law (UDL) of Qi et al, and are compared with CPPM values and found to be in good agreement. A comparison of half-life for ground and excited systems reveals that probability of decay increases with a rise in temperature or otherwise, inclusion of excitation energy decreases the T_1/2 values.     

Excitation of phosphorescence of pyrene implanted into a photoconductive polymer

Methods of populating the lowest excited triplet state T ₁ of pyrene implanted into polystyrene (PS) or photoconductive polymer materials polymethylphenylsilane (PMPS), poly-N-epoxypropylcarbazole (PEPC), and poly-N-vinylcarbazole (PVK) are studied. Photoluminescence was excited in the first electron transition band of pyrene and the above photoconductive polymers. It is found that, at concentrations of 0.05–0.50 mol l^?1, pyrene is effective in quenching the fluorescence of PMPS, PEPC, and PVK but has only a slight effect on the photoemission efficiency of geminate electron-hole pairs. As a result, the phosphorescence of pyrene in photoconductive polymers is excited both by the intersystem crossing from the first excited singlet state (S ₁ ? T ₁) and by the capture of triplet excitons created in the recombination of charge pairs. In addition, in PEPC and PVK, the phosphorescence of pyrene is excited by recombination of a captured hole with an electron. For this reason, the ratio of the quantum yields of phosphorescence and fluorescence of pyrene in photoconductive polymers is much larger than that in PS, wherein the T ₁ state of pyrene is populated by intersystem crossing S ₁ ? T ₁ only.     

Manifestation of nonplanarity effects and charge-transfer interactions in spectral and kinetic properties of triplet states of sterically strained octaethylporphyrins

Properties of the triplet states of octaethylporphyrins with the steric hindrance (free bases and Pd complexes) are studied by the methods of stationary and kinetic spectroscopy in the temperature range from 77 to 293 K. The mono-mesophenyl substitution results in a decrease in the quantum yield and shortening of the phosphorescence lifetime of Pd complexes by 250–3500 times in degassed toluene at 293 K. The phosphorescence quenching is caused by nonplanar dynamic conformations of the porphyrin macrocycle in the T ₁ state, which also lead to the appearance of new bands at λ～1000 nm in the T-T absorption spectra. As the number of meso-phenyls (Pd-octaetyltetraphenylporphyrin) increases, the quantum yield of phosphorescence further decreases (<10^?5) at 293 K, the lifetime of the T ₁ state shortens (<50 ns), and the efficiency of the singlet oxygen generation abruptly decreases (<0.01). The intense bathochromic emission of this compound at 705 nm with a lifetime of 1 ms at 77 K is assigned to the phosphorescence of a nonplanar conformation. Upon meso-orthonitrophenyl substitution, the quenching of phosphorescence of Pd complexes (by more than 10⁴ times at 293 K) is caused by direct nonadiabatic photoinduced electron transfer from the T ₁ state to the nearest charge-transfer state with the probability k _et ^T =(1.5–4.0)×10⁶ s^?1. The induced absorption of ortho-nitro derivatives in the region between 110 and 1400 nm is caused by mixing of pure ππ* states with charge-transfer states.     

Covalence-induced stabilization of an intermediate-spin state and the magnetic susceptibility of LaCoO<Subscript>3</Subscript>

The energies of terms with spins S = 0, 1, 2 have been found using exact diagnoalization of the multielectron Hamiltonian of a multiband pd model for the CoO₆ cluster. Co (e _g orbital)-O hops, which form the covalent σ bond, are shown to decrease the energy of the state (IS) with an intermediate spin (S = 1) as compared to the energy of the state (LS) with a low spin (S = 0). An analogue of the Tanabe-Sugano diagram that takes into account the covalence of the CoO₆ cluster is constructed. The state with S = 1 is shown to be a ground state at certain model parameters. An increase in temperature is established to decrease the crystal field and, thus, favors the transition of the ground state from LS to IS at T = 100 K and the transition of the IS ground state to a state (HS) with a high spin (S = 2) at T = 550 K. The magnetic susceptibility of LaCoO₃ is calculated with allowance for the LS, IS, and HS states and for the fact that the HS state exhibits threefold orbital degeneracy of the t _2g shell, which results in an effective orbital moment L = 1 and the importance of spin-orbit interaction. The behavior of this magnetic susceptibility agrees well with the experimental x(T) dependence of LaCoO₃.     

Fine-structure phosphorescence and radiative deactivation of the lowest triplet states in the most toxic dioxins

The transition dipole moments for the transition T₁(ππ*) → S₀ to vibrational energy levels of the nontotally symmetric vibrational modes of 2,3,7,8-tetrachloro-and 1,2,3,7,8-pentachlorodibenzo-p-dioxins are calculated. The interpretation of the fine-structure phosphorescence spectrum of the first of these compounds is refined, and the radiative deactivation rate constants for the s sublevels of the lowest triplet state T₁ are estimated. For a number of polychlorinated compounds, the effect of chlorine atoms occupying the α and β positions in a molecule on the T^s → S₀ transition dipole moments is discussed.     

Spin-selective low temperature spectroscopy on single molecules with a triplet-triplet optical transition: Application to the NV defect center in diamond

The spin-selective photokinetics of a single matrix-isolated impurity molecule with a triplet-triplet optical transition, T ₀–T ₁, is considered and the manifestations of the photokinetics in the fluorescence excitation spectra and intensity autocorrelation functions g ⁽²⁾(τ) of the molecule undergoing narrow-band optical excitation is studied to resolve the fine structure of the transition. The rates of intersystem crossings (ISCs) T ₁→S→T ₀ to and from a nonradiating singlet state S of the molecule and the rate of population relaxation among the ground (T ₀) state sublevels can be obtained from the spectra and g ⁽²⁾(τ) using the analytical expressions obtained. New experiments on an individual NV defect center in nanocrystals of diamond, where, for the first time, the fine structure of its triplet-triplet ³ A-³ E zero-phonon optical transition (~637 nm) at 1.4 K was resolved, are interpreted. It is concluded that the rate of the ISC transition from the m _S =0 sublevel of the excited ³ E state to the singlet ¹ A state (~1 kHz) is much slower than the rates from the m _S =±1 substates, while the rates of ISC transitions to different m _S substates of the ground ³ A state are close to each other (~1 Hz). As a result, only the optical transition between m _S =0 sublevels in the ³ A-³ E manifold contributes strongly to the fluorescence. The experimentally observed double-exponential decay of the g ⁽²⁾(τ) function is explained by the two pathways available to the center for it to leave the S state: (i) the S→ T ₀(m _S )=0) transition and (ii) the S→T ⁰(m _S =±1) transitions followed by the slow spin-lattice relaxation T ₀(m _S =±1)→T ₀(m _S =0) (rate ~0.1 Hz). The work is important for studies where the NV center is used as a single photon source or for quantum information processing.     

Integral characteristics of vibronic-spin-orbit interactions in a phosphorus-containing analogue of the fluorene molecule

The strengths (P ₀₀ ^s )² and F _VSO ² of the transitions from the triplet sublevels s = z, y, and x of the electronic state ³A″ of the phenyldibenzophosphole (DB(P-Ph)) molecule are calculated taking into account the intramolecular spin-orbit (SO) and joint vibronic-spin-orbit (VSO) interactions. The contributions to the vibronic transition strengths from the SO interactions in different structural elements of the molecule (the C atoms of the dibenzene framework, the P atom, and the Ph substituent) are determined. The effect of the nonplanar nuclear configuration of the DB(P-Ph) molecule on the values of F _VSO ^s is investigated. The radiative deactivation rate constants of the k _rad ^s triplet sublevels T ^s are estimated. It is found that the vibrations of the A′(B₁) symmetry in the fine-structure phosphorescence spectrum of DB(P-Ph) occur due to both the SO coupling exclusively in the P atom and the T ^x → S₀ transition (the x axis is perpendicular to the planar dibenzene framework of the molecule) with a high (preferential) population of this triplet sublevel.     

Intensity of singlet-triplet transitions in C<Subscript>60</Subscript> fullerene calculated on the basis of the time-dependent density functional theory and taking into account the quadratic response

The singlet-singlet and triplet-triplet absorption spectra of C₆₀ fullerene are calculated using the density functional method and taking into account the theory of linear and quadratic responses. The B3LYP density functional and the 6–31G and 3–21G atomic basis sets are used. The calculations are performed using the D_2h and D_5d symmetry groups, although the real symmetry of the ground state is described by the I _h symmetry group. The matrix elements of the operator of the spin-orbit coupling are calculated and the probabilities of some singlet-triplet transitions are estimated. Taking into account the data in the literature on vibronic interactions of vibrations of the t_1u, t_2u, g _u , and h _u symmetry species, the radiative lifetime of the 1³T_2g → 1¹A _g phosphorescence was estimated to be 45 s. The fact that this time proved to be considerably greater than the experimentally observed total lifetime of the triplet testifies to a fast nonradiative deactivation of the lowest triplet state of C₆₀ fullerene and agrees with a low phosphorescence intensity. The zero-field splitting of some triplets and the intensities of magnetic dipole transitions are discussed.     

The nature of the lower excited state of the special pair of bacterial photosynthetic reaction center of <Emphasis Type="Italic">Rhodobacter Sphaeroides</Emphasis> and the dynamics of primary charge separation

Quantum-chemical calculations of the structure in the ground and lower singlet excited states and the vibrations (in the ground state) of special pair P of photosynthetic reaction center of purple bacteria (RCPb) Rhodobacter Sphaeroides, consisting of two bacteriochlorophyll molecules P_A and P_B, have been carried out. It is shown that excitation of the special pair is followed by fast relaxation dynamics, accompanied by the transformation of the initial P* state into the P_A^δ+P_B^δ- state (δ ~ 0.5) with charge separation. This behavior is due to the presence of several nonplanar vibrations with participation of the acetyl group of macrocycle P_В in the nuclear wave packet on the potential surface of the P* state; these vibrations facilitate destabilization of the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) of the macrocycle P_A and formation of the P_A^δ+P_B^δ- state. The structural transformations in the P* state are due to its linking character in the contact region of the acetyl group-containing pyrrole rings of P_A and P_B. The transition from the P* state to specifically the P_A^δ+P_B^δ- state is related to the fact that the acetyl group P_A is involved in the intermolecular hydrogen bond with amino acid residue His^L168; for this reason, this group and the pyrrole ring linked with it can hardly participate in structural transformations. The electronic matrix element Н₁₂ of the electron transfer from the special pair in the P_A^δ+P_B^δ- state to a molecule of accessory bacteriochlorophyll В_А greatly exceeds that for the transfer to В_B. This circumstance and the fact that the P_A^δ+P_B^δ- state is energetically more favorable than the P* state facilitate the preferred directionality of the electron transfer in RCPb Rhodobacter Sphaeroides with participation of the cofactors located in its subunit L.     

Formation of textured Ni(200) and Ni(111) films by magnetron sputtering

The effect of the working gas pressure (P ≈ 1.33–0.09 Pa) and the substrate temperature (T_s ≈ 77–550 K) on the texture and the microstructure of nickel films deposited by magnetron sputtering onto SiO₂/Si substrates is studied. Ni(200) films with a transition type of microstructure are shown to form at growth parameters P ≈ 0.13–0.09 Pa and T_s ≈ 300–550 K, which ensure a high migration ability of nickel adatoms on a substrate. This transition type is characterized by a change of the film structure from quasi-homogeneous to quasi-columnar when a film reaches a critical thickness. Ni(111) films with a columnar microstructure and high porosity form at a low migration ability, which takes place at P ≈ 1.33–0.3 Pa or upon cooling a substrate to T_s ≈ 77 K.     

Topology of the Fermi surface and the coexistence of orbital antiferromagnetism and superconductivity in cuprates

It has been shown that the strong coupling model taking into account a rise in the spin antiferromagnetic insulating state explains the doping dependence of the topology and shape of the Fermi contour of superconducting cuprates. Hole pockets with shadow bands in the second Brillouin zone form the Fermi contour with perfect ordinary and mirror nesting, which ensures the coexistence of orbital antiferromagnetism and superconductivity with a large pair momentum for T < T_C. The weak pseudogap region (T_* < T < T*) corresponds to the orbital antiferromagnetic ordering, which coexists with the incoherent state of superconducting pairs with large momenta in the strong pseudogap region (T_C < T < T_*).     

Radiative deactivation of the lowest triplet state of dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxine

A theoretical evaluation of the dipole moments of vibronic transitions (which are governed by vibronic spin-orbit interactions) was carried out for dibenzo-p-dioxin molecules. On the basis of the comparison of the obtained results with the data on the distribution of line intensities in a fine-structure phosphorescence spectrum of dibenzo-p-dioxin at 4.2 K, it is inferred that radiative deactivation of the lowest triplet state T ₁ (ππ*) occurs from one of the triplet sublevels. For the molecules of dibenzo-p-dioxin and one of the isomers of tetrachlorodibenzo-p-dioxin, the effect of the form of vibrational modes and individual constants of the spin-orbit coupling in O and Cl atoms on vibronic spin-orbit interactions is discussed.     

The effect of the nonplanarity of heterocyclic analogues of fluorene with the phosphorus atom on spin-orbit interactions

The transition dipole moments P ₀₀ ^S for the transitions from the sublevels s=z,y, and x of the triplet electronic states ³ A″, which are caused by intramolecular spin-orbit (SO) interactions, are calculated. The calculation is carried out for molecules of heterocyclic analogues of fluorene containing phosphorus and nitrogen (namely, the groups P-H, P-C₆H₅, and N-H). The influence that the planar and nonplanar models of the molecules, as well as the substituents ?C₆H₅ and ?H at the heteroatom (HA), exert on the values of (P ₀₀ ^S )² and on the directions of the corresponding vectors is considered. The values of the component \(k_{SO^ \sim } \sum _s (P_{00}^s )^2 \) of the radiative deactivation rate constant of the T ₁ state are calculated. It is ascertained that, in the series of molecules with HA = N, O, P, and S, both the calculated values of k _SO and those experimentally determined from an analysis of the intensity distribution in fine-structure phosphorescence spectra vary little, whereas the constant of the SO coupling in the heteroatom ?_HA increases substantially along this series. The reason for the weak influence of ?_HA on values of k _SO—common for both planar and nonplanar molecules—is found.     

Doppelkonversion

An excited nuclear state can decay by three different modes of double quantum emission, namely doubleγ-emission,γ-electron emission and double conversion electron emission. The emission of twoγ-quanta has been considered in an earlier paper¹. The purpose of the present work is to treat all three processes together in a systematic manner. It is shown that the connection between the transition rates forγ-electron emissionT _γc and doubleγ-quantum emissionT _γγ is more complicated than in the case of single quantum processes. However,T _γc can still be expressed in terms of the usual conversion coefficients. This is also true for the transition rate T_cc for the emission of twoK-shell electrons, although only approximately. For the emission of electrons from different atomic shells the formulas become rather complicated, because of interference effects. The electron andγ-quantum spectra in all of the three second order processes are discussed in detail for the decay of the isomeric level in Xe¹³¹.     

Investigating the Double Beta Decay of <Superscript>58</Superscript>Ni

Double beta decay (β + EC, EC/EC) of ⁵⁸Ni is investigated at France’s Modane Underground Laboratory (4800 m water equivalent) using the OBELIX ultralow-background HPGe detector with a sensitive volume of 600 cm³ and a natural nickel sample of ~68% 58Ni with a mass of ~21.7 kg. After preliminary analysis of the experimental data accumulated over ~144 days, new experimental limits are obtained for the 2νβ⁺EC decay of ⁵⁸Ni to the 0⁺ ground state and the 2 ₁ ⁺ , 811 keV excited state of ⁵⁸Fe, and for the 2νEC/EC decay of ⁵⁸Ni to the 2 ₁ ⁺ , 811 keV and 2 ₂ ⁺ , 1675 keV excited states of ⁵⁸Fe. The limits are T_1/2(β⁺EC,0→0⁺) > 1.7 × 10²² yr, T_1/2(β⁺EC,0→2 ₁ ⁺ ) > 2.3 × 10²² yr, T_1/2(EC/EC,0→2 ₁ ⁺ ) > 3.3 × 10²² yr, and T_1/2(EC/EC,0→2 ₂ ⁺ ) > 3.4 × 10²² yr. Experimental limit T_1/2(0νEC/EC–res, 1918 keV > 4.1 × 10²² yr is obtained for resonant neutrinoless radiative EC/EC decay with an energy of 1918.3 keV. All limits are at 90% CL.     

Effect of phase transitions on the exciton absorption spectrum of Rb<Subscript>x</Subscript>K<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ag<Subscript>4</Subscript>I<Subscript>5</Subscript> superionic conductors

The absorption spectrum of thin films of solid solutions of Rb_xK_1?xAg₄I₅ superionic conductors is investigated in the energy range 3–6 eV at temperatures from 90 to 290 K upon heating and cooling. It is established that the temperature dependences of the spectral position E _m and the half-width Γ of the long-wavelength exciton band are determined by the exciton-phonon interaction and the generation of Frenkel defects at phase transitions to the superionic state. Fluctuations of the composition of solid solutions do not affect the behavior of the dependences E _m (x) and Γ(x) at 90 K, which is indicative of the localization of excitons in the AgI sublattice of these compounds. A difference in the dependences T _c 1(x) and T _c 2(x) (the γ → β and β → α phase transitions, respectively) is revealed: the curve T _c 1(x) has a minimum at x ≈ 0.5, whereas the curve T _c 2(x) shows a weak maximum.     

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.