Electronic structure and intramolecular photophysical processes of cations of symmetric indopolycarbocyanine dyes

The electronic structure, spectra, and rate constants of radiative and nonradiative processes of cations of the vinylogous series of symmetric indopolycarbocyanine dyes are calculated by the semiempirical method of partial neglect of differential overlap. The S ₀ → S _n absorption spectra are interpreted. The dependences of the efficiency of the deactivation of the fluorescent state on the length of the polymethine chain of cations are analyzed. The quantum yields of the fluorescence from the first and second singlet states are calculated. The calculation results agree satisfactorily with experimental data.     

Electronic structure and fluorescent properties of malononitrile-based merocyanines with positive and negative solvatochromism

The behavior of the positions and shapes of the fluorescence bands of di-, tetra-, and hexamethine merocyanine dyes with 3H-indolyliden (dyes 1–3) and benzoimidazolyliden (dyes 4–6) as electron-donating substituents and malononitrile as an electron-accepting substituent is studied by the method of moments in solvents of different polarity. The solvatofluorochromic shifts have been found to be smaller than the solvatochromic shifts not only for negatively solvatochromic merocyanines 4–6, but also for dyes 1–3 whose solvatochromism is positive. For dyes 4–6, cases of a change of the sign of solvatofluorochromism with respect to the sign of solvatochromism are revealed. These nontrivial effects are accounted for by transitions between the polyene and polymethine electronic structures of merocyanines in the fluorescence state S ₁ that occur with increasing medium polarity. In contrast to the absorption spectra of merocyanines 1–3, an increase in the chain length results in an increase in the vinylene shifts in the fluorescence spectra of these dyes, as well as in a decrease in the deviations and in the narrowing of the bands. This is explained by the fact that the electronic structure of these merocyanines in the S ₁ state is closer to that of the ideal polymethine (the cyanine limit) than in the S ₀ state. The fluorescence bands of merocyanines 4–6 are observed to be broader compared to the absorption bands. This broadening is caused by a change in the relation between intermolecular and vibronic interactions during absorption and emission of light. The interactions of these types have a decisive effect on the behavior of the Stokes shifts and fluorescence quantum yields of merocyanines 1–6.     

Theoretical Analysis of the Fluorescence Spectra of 7-Azaindole and Its Tautomer

The electronic—vibrational fluorescence spectra of the first, S₀ → ¹L_b, and second, S₀ → ¹L_a, electronic transitions of 7-azaindole and its tautomer for an isolated state have been calculated. Specific features of structural changes in 7-azaindole and its tautomer upon electronic excitation are determined. Vibrational spectra are assigned for the ground state, and the vibrational structure of fluorescence spectra is interpreted. It is shown that the intensity redistribution between the 6a and 6b oscillations, which is observed in the fluorescence spectrum of the S₀ → ¹L_b transition in 7-azaindole, can be explained as a result of intensity borrowing (according to the Herzberg—Teller mechanism) from the ¹L_a state.     

Intramolecular proton transfer from the highest singlet states in 3-hydroxyflavone

It is found that the excitation spectra of the dual fluorescence of 3-hydroxyflavone are different for different recording wavelengths and that the intensity ratio of the emission of the normal and tautomeric (with intramolecular proton transfer) forms upon selective UV excitation in the regions of the S ₁, S ₂, and S ₃ singlet absorption bands strongly depends on the excitation wavelength. The results obtained directly point to the existence of an additional channel of population of the excited state of the tautomeric form and are explained by the intramolecular proton transfer through the S ₂ and S ₃ excited singlet states of fluorophore molecules. The constants of this transfer are estimated using analytical relations for the steady-state fluorescence excitation.     

Broadening of a two-photon resonance in a zinc atom in collisions with CO<Subscript>2</Subscript>, CO,and NO molecules

The broadening of a two-photon resonance is studied experimentally at the 4s¹S₀?6s³S₁ transition in a zinc atom upon absorption of two waves with a small detuning from an intermediate state in collisions with CO₂, CO, and NO molecules. The measured absolute values of broadening cross sections greatly exceed gas-kinetic cross sections and are (9.4±2.4, 6.5±1.6, and 3.9±1.0)×10^{? 14}cm² for CO², CO, and NO, respectively. Anomalously large rate constants and cross sections obtained in experiments are explained by the efficient resonance quenching of the excited states of zinc atoms in collisions with molecules accompanied by transfer of the energy of excited atoms to vibrational-rotational degrees of freedom of molecules.     

Excitation of resonance lines of the cadmium ion by monoenergetic electrons

The excitation of resonance lines at 226.5 and 214.4 nm, corresponding to the transitions 226.5 (5p ² P ₁ ^2/0 →5s ² S _1/2) and 5p ² P ₃ ^2/0 → 5s ² S _1/2, respectively, in the Cd⁺ ion upon collisions with monoenergetic electrons with an energy in the range of 4–130 eV is studied with high precision by a spectroscopic method in crossing beams. It is found that the dependence of the effective excitation cross sections of the resonance doublet components on the energy of the electrons has a distinct resonance structure. It is shown that the dominant mechanism responsible for this structure is the capture of an incident electron by a Cd⁺ ion with the simultaneous excitation of an electron from the subvalence 4d ¹⁰ shell to the autoionizing states of the Cd atom with their subsequent decay (directly or via cascade transitions) to resonance levels of the ion. The results obtained are compared with data from other experiments and with the results of the R-matrix strong-coupling calculation of 15 states and of semiempirical calculation using the Van Regemorter formula.     

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.     

Dominant decays of scalar leptoquarks and scalar gluons in the minimal four-color symmetry model

Fermionic and weak decays of the scalar leptoquarks S = S ₁ ⁽⁺⁾ , S ₁ ^(?) , and S _m and the scalar gluons F = F ₁ and F ₂ predicted by the minimal model involving four-color symmetry and the Higgs mechanism of quark-and lepton-mass splitting are considered. The widths and the branching ratios are calculated for these decays, and the results are analyzed versus the couplings and masses of decaying particles. It is shown that, at relatively small mass splittings Δm within scalar doublets (Δm < m _W), the fermionic decays S ₁ ⁽⁺⁾ → tl _j ⁺ , S ₁ ^(?) → v _i \(\tilde b\), S _m → t \(\tilde \nu \) _j, F ₁ → t \(\tilde b\), and F ₂ → t \(\tilde t\), which are characterized by few-GeV widths for m _S, m _F < 1 TeV and decay branching ratios close to unity, are dominant, but that, for Δm > m _W, the weak decays S → S′W and F → F’W compete with the above fermionic decays. In the case of m _S < m _t, the processes S ₁ ⁽⁺⁾ → cl _j ⁺ , S ₁ ^(?) → v _i \(\tilde b\), S _m → bl _j ⁺ , and S _m → c \(\tilde \nu \) _j, whose total branching ratios are Br(S ₁ ⁽⁺⁾ → cl ⁺) ≈ Br(S ₁ ^(?) → v \(\tilde b\)) ≈ 1, Br(S _m → bl ⁺) ≈ 0.9, and Br(S _m → c \(\tilde \nu \)) ≈ 0.1, appear to be dominant decays of scalar leptoquarks. Searches for these decays at LHC and the Tevatron are of interest.     

The <Emphasis Type="Italic">HZZ</Emphasis>′ Coupling and the Higgs-Strahlung Production <Emphasis Type="Italic">pp</Emphasis> → <Emphasis Type="Italic">ZH</Emphasis> at the LHC

The Higgs-strahlung production process pp → Z′ → ZH is an important process for studying the HZZ′ interaction. We take the B ? L model and the nonuniversal S U(2)₁ × S U(2)₂ × U(1) _Y model as two examples and investigate their correction effects on ZH production at the LHC. Our numerical results show that, considering constraints on these two new physics models, the contributions of the B ? L model to the ZH production cross section are very small, while the S U(1)₁ × S U(2)₂ × U(1) _Y model can generate significant contributions.     

Collision frequency shift of hyperfine transitions in atomic hydrogen at a low temperature

The experimental results on the collision frequency shift of ESR in diluted two-and three-dimensional atomic hydrogen at ultralow temperature have been analyzed. The apparent contradiction between experiment and theory is resolved by taking into account the relation between the symmetry of the state of two atoms and their total electron spin S. For example, transitions between symmetric and antisymmetric states of a pair of atoms induced by a symmetric perturbation are forbidden. If symmetric and antisymmetric states are, respectively, pure electronic triplets (S= 1) and singlets (S = 0), this results in the cancellation of the singlet-triplet transitions. Thus, the collision frequency shift of b → c and b → a transitions vanishes in a completely electron and nuclear spin-polarized gas (hyperfine state b). The comparison is performed with experiments in ultracold alkali vapors.     

Morphological transformations of diblock copolymers in binary solvents: A simulation study

Morphological transformations of amphiphilic AB diblock copolymers in mixtures of a common solvent (S1) and a selective solvent (S2) for the B block are studied using the simulated annealing method. We focus on the morphological transformation depending on the fraction of the selective solvent C _S2, the concentration of the polymer C _p , and the polymer–solvent interactions ε _ij (i = A, B; j = S1, S2). Morphology diagrams are constructed as functions of C _p , C _S2, and/or ε _AS2. The copolymer morphological sequence from dissolved → sphere → rod → ring/cage → vesicle is obtained upon increasing C _S2 at a fixed C _p . This morphology sequence is consistent with previous experimental observations. It is found that the selectivity of the selective solvent affects the self-assembled microstructure significantly. In particular, when the interaction ε _BS2 is negative, aggregates of stacked lamellae dominate the diagram. The mechanisms of aggregate transformation and the formation of stacked lamellar aggregates are discussed by analyzing variations of the average contact numbers of the A or B monomers with monomers and with molecules of the two types of solvent, as well as the mean square end-to-end distances of chains. It is found that the basic morphological sequence of spheres to rods to vesicles and the stacked lamellar aggregates result from competition between the interfacial energy and the chain conformational entropy. Analysis of the vesicle structure reveals that the vesicle size increases with increasing C _p or with decreasing C _S2, but remains almost unchanged with variations in ε _AS2.     

Manifestation of the vibronic analogue of the Fermi resonance in quasi-line spectra of porphyrins: Experiment and theoretical analysis

The quasi-line low-temperature (4.2 K) fluorescence excitation spectra of two porphyrins, meso-tetraazaporphin and meso-tetrapropylporphin introduced into an n-octane matrix are measured in the range of the S ₀ → S ₂ electronic transition. A characteristic feature of these spectra is that a conglomerate of quasi-lines—a structured complex band—is observed instead of one 0–0 quasi-line of the S ₀ → S ₂ transition. In this band, the intensity distributions for the two main types of impurity centers considerably differ from each other. The occurrence of such conglomerates is interpreted as a result of nonadiabatic electronic-vibrational interactions between vibronic S ₂ and S ₁ states (the complex vibronic analogue of the Fermi resonance). The frequencies and intensities of individual transitions determined from the deconvolution of complex conglomerates are used as the initial data for solving the inverse spectroscopic problem: the determination of the unperturbed electronic and vibrational levels of states involved in the resonance and the electronic-vibrational interaction matrix elements between them. This problem is solved with a method developed previously. The energy intervals between the S ₂ and S ₁ electronic levels of the two main types of impurity centers formed by molecules of a given porphyrin in the crystal matrix are found to significantly differ from each other (～100 cm^?1). At the same time, the energies of the unperturbed vibrational states of the S ₁ electronic level partcipating in the resonance are very close to each other for these two types of impurity centers.     

Excitonic representation: Collective excitation spectra in the quantized Hall regime and spin biexciton

The excitonic representation method for describing collective excitations in the quantized Hall regime makes it possible to simplify analysis of the spectra and to obtain new results in the strong magnetic field limit, when E _C ??ω_c (ω_c is the cyclotron frequency and E_C is the characteristic Coulomb energy). For an integer odd filling factor ν greater than unity (i.e., for ν = 3, 5, 7,...), the spectra of one-cyclotron magneto-plasma excitations are calculated. For unit filling factor, the existence of a spin biexciton (bound state of two spin waves) corresponding to excitation with a spin change (δ_S = δ_Sz = ?2) is proved. The exact equation determining the ground state of the biexciton is derived in the thermodynamic limit N_Φ → ∞ (_N? is the system degeneracy). The exchange energy of this state is lower than for a single spin wave (with δ_S = δ_Sz = ?1) for the same value of the 2D wavevector q. In the limit q → ∞ corresponding to the decay of a biexciton into a pair of quasiparticles one of which is a trion with a spin of ?3/2, the energy is found to be lower than the energy (e²/εl _B )√π/2 required for exciting an electron-hole pair in the strictly 2D case (l_B is the magnetic length and ε is the dielectric constant), although this energy is higher than another “classical” result (e²/εl _B )√π/2, corresponding to the excitation of a skyrmion-antiskyrmion pair (|δS|=|δS _z |?1). The solution of the exact equation gives the trion binding energy and the activation gap for quasiparticles whose excitation corresponds to a change in the total spin by δS = δ S_z =?3. The energy of a spin biexciton is calculated for values of the wavevector such that ql _B ?1.     

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.     

Fluorescence and picosecond induced absorption from the lowest singlet excited states of quercetin in solutions and polymer films

The spectroscopic and photophysical properties of the biologically important plant antioxidant quercetin in organic solvents, polymer films of polyvinyl alcohol, and a buffer solution at pH 7.0 are studied by stationary luminescence and femtosecond laser spectroscopy at room temperature and 77 K. The large magnitude of the dipole moment of the quercetin molecule in the excited Franck–Condon state μ _e ^FC = 52.8 C m indicates the dipolar nature of quercetin in this excited state. The transient induced absorption spectra S ₁→S _n in all solvents are characterized by a short-wave band at λ _abs ^max = 460 nm with exponential decay times in the range of 10.0–20.0 ps. In the entire spectral range at times of >100 ps, no residual induced absorption was observed that could be attributed to the triplet–triplet transitions Т ₁ → Т _k in quercetin. In polar solvents, two-band fluorescence was also recorded at room temperature, which is due to the luminescence of the initial enol form of quercetin (~415 nm) and its keto form with a transferred proton (550 nm). The short-wave band is absent in nonpolar 2-methyltetrahydrofuran (2-MTHF). The spectra of fluorescence and fluorescence excitation exhibit a low dependence on the wavelength of excitation and detection, which may be related to the solvation and conformational changes in the quercetin molecule. Decreasing the temperature of a glassy-like freezing quercetin solution in ethanol and 2-MTHF to 77 K leads to a strong increase in the intensity (by a factor of ~100) of both bands. The energy circuits for the proton transfer process are proposed depending on the polarity of the medium. The main channel for the exchange of electronic excitation energy in the quercetin molecule at room temperature is the internal conversion S ₁ ? S ₀, induced by the state with a proton transfer.     

Two-photon Rydberg resonances in lithium-7 obtained by recording reduction of resonance fluorescence

In a magneto-optical trap (MOT) of ⁷Li, two-photon Rydberg resonances are recorded by using a spectroscopic technique, which based on variation in the resonance fluorescence. The first excitation frequency is detuned by 0.59 GHz from the intermediate 2P _3/2 state. Two counter-propagating laser beams are used. The resonances are studied on two-photon transitions 2S _1/2 ? nl in a range of principal quantum number n from 38 to 120. The widths of the observed resonances are varied from 4.4 to 13 MHz for different MOT parameters.     

Mechanisms of ionization of <Emphasis Type="Italic">F</Emphasis><Subscript>2</Subscript>-centers in laser media on the basis of LiF crystals

F₂ color centers with a superhigh concentration (5000-cm^–1 absorption coefficient at 450 nm) were formed by high-density electron beams in a layer of LiF crystals of micrometer thickness. The F₂-centers excited by high-power nanosecond wide-band optical pulses (the “soft” pumping regime) efficiently amplified the laser radiation and showed high stability under these conditions. A low stability of F₂-centers to laser radiation (the “hard” excitation regime) is explained by the dissociation of (F ₂ ⁺ , F^–) pairs induced by two-step ionization of F₂-centers: (2hν > 4.5 eV) → F₂ → (F₂)* → F ₂ ⁺ + e; F + e → F^–; F ₂ ⁺ + F^– → 3F.     

Estimating of CP-violation in <Emphasis Type="Italic">B</Emphasis><Superscript>0</Superscript>→ψ(2<Emphasis Type="Italic">S</Emphasis>)π<Superscript>0</Superscript> decay

I present estimates of CP-violating asymmetries in the non-leptonic charmonium two-body B⁰→ψ(2S)π⁰ decay and the same decays of B⁺→ψ(2S)π⁺ and B⁺→ψ(2S)K⁺ These estimates are based on QCD and improved QCD factorization approach making use of next-to-leading order (NLO) contributions. The CP-violating asymmetry for B⁰→ψ(2S)π⁰ decay is not available, according to the same calculations, it is expected if it can be measured in the future its value will be S_ψ(2S)π0(B⁰ → ψ(2S)π⁰)= 0.662 ± 0.197 and C_ψ(2S)π0(B⁰ → ψ(2S)π⁰)= 0.024 ± 0.007.     

Photoluminescence of Ca(Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>S<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript> compounds

Photoluminescence (PL) observed in solid solutions of Ca(Al _x Ga_1–x )₂S₄:Eu²⁺ (x = 0.1–0.3) is studied. It is shown that the increase in emission intensity by 18% is caused by changes in the x values and electronic 5d → 4 f transitions in Eu²⁺ ions. A change in the position of the emission spectrum or its partial shift toward shorter wavelengths is due to an increase in the aluminum concentration and a decrease in the crystal field energy. The energy of the zero phonon line E ₀, redshift D, and the Stokes shift ΔS are determined. A decrease in the photoluminescence intensity maximum and an increase in the half-width of the spectrum are found in the temperature range of 10–300 K. The efficiency of emission at temperatures of 20 and 300 K is almost independent of the excitation power density of up to ~10⁴ W/cm². The luminescence lifetime of Eu²⁺ ions was 383, 357, 346, and 333 ns for x = 0, 0.1, 0.2, and 0.3, respectively.     

Manifestation of the Coster-Kronig effect in the near-threshold electron-impact excitation of the Cd<Superscript>+</Superscript> ion

The near-threshold portions of the energy dependences of the effective excitation cross sections of the resonance transition 4d¹⁰5p²P_1/2° → 4d¹⁰5s²S_1/2 and the two-electron forbidden transition 4d⁹5s²²D_5/2 → 4d¹⁰5p²P_3/2° in the spectrum of the Cd⁺ ion were investigated by the spectroscopic method in crossed electron and ion beams. In the region of energy splitting of the ²P° and ²D levels, a significant resonance contribution of the autoionizing states of cadmium (decaying during the Coster-Kronig process) to the effective excitation cross sections of the noted transitions was revealed for the first time. It is found that the resonance contribution manifests itself much more strongly for the forbidden transition in comparison with the more intense resonance transition; i.e., the manifestation of the Coster-Kronig effect in the electron excitation of ions depends strongly on the cross section of the direct process. It is ascertained that, during the Coster-Kronig process, the main contribution to the resonance excitation of both the resonance and the two-electron forbidden spectral transitions is from the low-lying terms of the series of autoionizing states 4d¹⁰5p(²P_3/2°)ns, md and 4d⁹(²D_3/2)5s²ns, md, which are in the splitting region of the ²P_{1/2, 3/2}° and ²D_{5/2, 3/2} levels, rather than from the high-lying atomic autoionizing states of cadmium, which are located near the ionization limits (corresponding to the and ²P_3/2° and ²D_3/2 levels).