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.     

Model and calculation of rate constants of nonradiative <Emphasis Type="Italic">T-S</Emphasis> intersystem conversion: Test by example of naphthalene and its chlorine derivatives

For in-plane spin states (s = z, y), the rate constants K _dg ^s of the nonradiative energy degradation T ₁ ⇝ S ₀ of the lowest triplet T ₁ state of naphthalene (NPH) and its dichloro-substituted derivatives at positions 1,4- and 2,3- of the molecule (1,4-NPH and 2,3-NPH) are calculated. A simple model is proposed for calculations that is based on the nonadiabatic approximation and uses all the out-of-plane vibrational modes of the molecule as promoting vibrational modes. As a result of calculations, the dependences of the rate constants K _dg and K _dg ^s on the positions of chlorine atoms in the molecule are obtained, which are consistent with the known data of magnetooptical measurements. The inversion of the ratio K _dg ^z : K _dg ^y in the 1,4-NPH and 2,3-NPH molecules is established.     

Nonradiative deactivation of the lowest triplet state of tetrachlorodibenzo-p-dioxin

In the nonadiabatic approximation, we have studied how the shape of promoting out-of-plane vibrational modes and vibronically induced spin-orbit interactions in structural elements of the 2,3,7,8-tetrachlorodibenzo-p-dioxin molecule affect the energy degradation rate constants K _dg ^s of triplet T ₁ ^s sublevels.     

Role of structural elements of chloronaphthalene molecules in spin-orbit coupling: Phosphorescence

The dipole moments (P ^s ) of the T ₁ ^S → S ₀ transition from the triplet sublevels s = z, y, x, which are determined by the spin-orbit (SO) coupling, are studied for a series of mono- and dichloro derivatives of naphthalene. Based on the model calculations, the effects of different factors (SO coupling in individual chlorine atoms occupying the α and β positions in the molecule, SO coupling in the carbon backbone of the molecule, and the compensation effect caused by the interference of SO interactions in individual structural elements of the molecule) on P ^s are differentiated and discussed.     

Roles played by an oxygen atom and out-of-plane high-frequency vibrational modes of a dibenzofuran molecule in the nonradiative deactivation of the lowest triplet state

We have studied the deactivation of the triplet sublevels s = z, y, and x of the lowest triplet state T ₁ ^s of the dibenzofuran molecule, which is determined by radiative (dipole) and nonradiative (degradation) transitions with the rate constants K _rad ^s and K _dg ^s . The main attention is paid to the nonradiative transitions T ₁ ^s ? S ₀ from the in-plane spin states (s = z, y), which are determined by the intramolecular interaction along the coordinates of out-of-plane vibrational modes. The roles played by the many-electron atom (oxygen) and high-frequency out-of-plane vibrational modes in the intramolecular interaction have been evaluated theoretically. Estimates of K _dg ^s based on three known approaches (three models) that describe the nonradiative transition in the approximation of adiabatic and nonadiabatic interactions are presented.     

A statistical analysis of the wavenumbers of triplet rovibronic transitions of the D<Subscript>2</Subscript> molecule: III. Optimum values of level energies

The optimum energy values of the vibrational-rotational levels of all the experimentally studied 35 triplet electronic states of the D2 molecule were found using a one-step optimization procedure only based on the Rydberg-Ritz combination and maximum likelihood principles. The set of energy values for 1050 levels was obtained from 3713 experimental data (3588 old and 125 new data) on the wavenumbers of rovibronic transitions. The energies were counted from the lowest vibrational-rotational level (ν = 0, N = 0) of the (1sσ2sσ)a ³Σ _g ⁺ electronic state. Errors in the empirical determination of optimum level energy values caused only by the limited consistency of the experimental data obtained by different authors, different methods, and in different spectrum regions were found. They are of 0.005–0.1 cm⁻¹ and increase as the vibrational and rotational quantum numbers grow. The possibility of discovery of new not identified earlier band systems was demonstrated. This can be done using the optimum level energies for calculations of the wave-numbers of spectral lines allowed by selection rules followed by the search for these lines in the experimental spectra of D₂.     

Spectroscopic and structural proprieties of LiAr and LiAr<Subscript>2</Subscript> molecules

We determined and tried to understand the spectroscopic and structural properties of small LiAr and LiAr₂ molecules within a simple model considering LiAr as a result of interaction between a valence electron and a LiAr⁺ molecular ion. Potential energy curves, spectroscopic constants, and vibrational levels corresponding to the Li(2s, 2p, 3s, and 3p)+Ar dissociation are reported for the LiAr molecule. The depth of the potential well for the X ²Σ⁺ ground state is found to be 50 cm⁻¹ (the corresponding experimental value is (42.5±1.2) cm⁻1 [1]). R _e is determined to be 9.36 a.u. (the experimental value is 9.24 a.u.). For the first excited state A, R _e = 4.97 a.u. and D _e = 993cm ⁻¹ (the corresponding experimental values are 4.68 a.u. and (925−40) cm⁻¹, respectively [1]). The spacing between the vibrational levels for the ground and first excited states is in very good agreement with the experiment. For the ground state, the difference between our results and the data of the most recent experiment is about 1 cm⁻¹. The model has been extended to study the LiAr₂ molecule in two forms (linear and triangular). We have determined the potential energy surfaces of the states dissociating to Li(2s, 2p)+Ar₂ and thus found the triangular form to be more stable as compared to the linear one. We have also calculated the transition energy between the ground state and first excited states of this molecule. The emission spectrum of the Li(2s)+Ar₂→Li(2p)+Ar₂ transition in both forms redshifts as compared to the Li(2s)→Li(2p) atomic transition.     

Effect of molecular structural elements of chloro-substituted derivatives of naphthalene on intramolecular interactions, which determine T1 ? S0 nonradiative transition

By calculating the matrix elements of operators of adiabatic and nonadiabatic interactions, which determine the process T ₁ ^S ↝ S ₀ in molecules of naphthalene and its 1,4- and 2,3-dichloro-substituted derivatives, we study how various factors of intramolecular interactions affect this process. The effects of α and β chlorine substituents on spin-orbit (SO) interactions in the carbon backbone of the molecule and in its chlorine atoms, where the compensation effect of SO interactions was revealed, are separated. It is found that high-frequency out-of-plane promoting modes (corresponding to vibrations of CCH groups) differently affect SO interactions in the carbon backbone of molecules and in chlorine atoms.     

Effect of extra liganding on spectral and kinetic characteristics and on quenching of excited states of multiporphyrin complexes by molecular oxygen

Based on studies of spectral and kinetic parameters of dimers of Zn porphyrins and of multiporphyrin self-assembling complexes formed on their basis, we find that extra liganding of dimers by pyridine inappreciably lowers the energy of the triplet level E(T ₁). We show that, in this case, the nonradiative deactivation T ₁ ↝ S ₀ of the electronic excitation energy of dimers Zn porphyrins increases not only due to increasing Franck-Condon factor. We discuss mechanisms of the quenching action of an extra ligand related to an accepting role played by high-frequency overtones of vibrations of extra ligand molecules, to an enhancement of the spin-orbit interaction due to energy lowering of σπ* states, and to out-of-plane distortion of dimers caused by the displacement of the Zn²⁺ ion out of the plane of the tetrapyrrole macrocycle. Quenching of triplet states of extra liganded dimers of Zn porphyrins by molecular oxygen in liquid solutions at 295 K depends on the character of donor-acceptor interactions with pyridine and rigidity of a linking molecular fragment. We find that the rate constants of oxygen quenching of the excited electronic states S ₁ and T ₁ of multiporphyrin complexes depend on their structure and composition, as well as steric hindrances, created by dimers (screening effects) for contact interactions of a π-conjugated system of the free base (extra ligand) with molecular oxygen. Screening effects of extra ligands by dimer molecules of Zn porphyrins, which reduce the oxygen quenching rate constants k _S and k _T , are found to barely affect the singlet-oxygen generation quantum yield γΔ.     

Semiempirical study of perturbations of the Landé g factors of electronic-vibrational-rotational levels of hydrogen: II. i 3 g − and j 3Δ g − states of the H2, HD,and D2 molecules

The values of the Landé g factors of the i ³Π _g ⁻ , v, N and j ³Δ _g ⁻ , v, N states of the H₂, HD, and D₂ molecules have been found semiempirically for the following vibrational and rotational quantum numbers: v≤3; N≤7 for H₂; N≤5 for HD; and N≤11 for D₂. These values were obtained in terms of the nonadiabatic model, which takes into account the interaction between the 3dπ³Π_g and 3dδ³Δ_g states with the same values of v and N in the approximation of pure precession, with the use of semiempirical values of the expansion coefficients of the wave functions in the Born-Oppenheimer basis determined by us previously and the results of numerical calculation of the overlap integrals of the vibrational wave functions of these states. The results obtained for the H₂ molecule are in good agreement with the data in the literature. For the i ³Π _g ⁻ and j ³Δ _g ⁻ states of the HD and D₂ molecules, the g factors were found for the first time. This made it possible to study for the first time the role of the isotopic effect in the perturbation of the dependences of the g factors of rovibrational levels on v and N for the triplet electronic states of the hydrogen molecule. It was found that the interference effects of interaction between the 3dπ³Π_g and 3dδ³Δ_g states lead both to significant differences—up to 8, 6, and 11 times for H₂, HD, and D₂, respectively (the i ³Π _g ⁻ state), 20 times for H₂ and HD, and two orders of magnitude for D₂ (the j ³Δ _g ⁻ state)—between the nonadiabatic values of the g factors and the corresponding adiabatic values for some isotopomers of the hydrogen molecule and to significant differences—up to 9 and 1.5 times for the j ³Δ _g ⁻ and i ³Π _g ⁻ states, respectively—in the nonadiabatic values of the g factors of rovibrational levels of different isotopomers of the hydrogen molecule. __________ Translated from Optika i Spektroskopiya, Vol. 96, No. 1, 2004, pp. 42–54. Original Russian Text Copyright ? 2004 by Astashkevich.     

The role of combined electron-deuteron screening ind-d fusion in metals

We propose that thed-d fusion rate in palladium can be enhanced by the combined screening of the electrostatic interactions by the itinerant deuterons and the conduction electrons. The model assumes that, under certain conditions, deuterium exists as a D⁺ ion in palladium. The combined screening by electrons and the D⁺ ions (deuterons) is found to be more effective than that due to electrons alone. The calculated values of thed-d fusion rates, considering screening, for composition PdD at 300 K are 10⁻¹⁶ s⁻¹ and 10⁻¹⁴ s⁻¹ for D ₂ ⁺ ion and D₂ molecule respectively. These values lie in the range suggested by the recent electrochemical experiments.     

The mechanism of formation of the hydroperoxyl radical in the CF<Subscript>3</Subscript>COOH + <Superscript>3</Superscript>O<Subscript>2</Subscript> system: a quantum-chemical study

Ab initio quantum-chemical calculations of the (CF₃CO₂H₂⁺…³O₂) and (CF₃CO₂⁻…³O₂) complexes were performed by the MP2 method. It was found that these complexes were characterized by low complex formation energies, of 2.97 and 1.72 kcal/mol, respectively. According to the MP2(full)/6-311++G(d, p) calculation data, the bridge stabilization of oxygen by linking with both the CF₃CO₂H₂⁺ cation and CF₃CO₂⁻ anion is much more favorable energetically. A study of the potential energy surface of the joint molecular system (CF₃CO₂H₂⁺…³O₂…CF₃CO₂⁻) shows that proton experiences activationless transfer from the cation to the ³O₂ molecule accompanied by electron transfer from the CF₃COO⁻ anion. An analysis of spin density distribution shows that two radicals are stabilized in the (CF₃CO₂….OOH….O=C(OH)CF₃) complex in the triplet state observed on the potential energy surface.     

The radiative characteristics of the rovibronic states of the hydrogen molecule: IV. Relative probabilities of the r 3Π g ? , s 3Δ g ? → c 3Π u ± spontaneous transitions of the H2 molecule

A statistical analysis of the available literature data and data obtained in this work on the wave numbers of the lines that appear in triplet-triplet rovibronic transitions of the H₂ molecule was performed. This allowed us to verify and refine the controversial identification of spectral lines and find the optimum rovibronic level energy values for the c ³Π _u ^±, r ³Π _g ⁻, and s ³Δ _g ⁻ states. The ratios between the line strengths of the P, Q, and R branches of the (4dπ)r ³Π _g ⁻, (4dδ)s ³Δ _g ⁻ → (2pπ)c ³Π _u ^± band systems of the H₂ molecule were measured systematically. The calculation results obtained in the Frank-Condon approximation differed substantially (by up to two orders of magnitude) from the experimental data. The dependences of the ratios between rovibronic line strengths of the r ³Π _g ⁻ → c ³Π _u ^± and s ³Δ _g ⁻ → c ³Π _u ^± transitions on the rotational quantum number N′ of the upper level were found to correlate with each other. The deviations of adiabatic theory increase as N′ grows, which is evidence of an important role played by electronic-rotational interactions in the perturbation of transition probabilities. The experimental ratios between the probabilities of rovibronic transitions satisfactorily agree with the results of calculations within the framework of the simple nonadiabatic model taking into account electronic-rotational interaction of radiating adiabatic states in the approximation of pure precession. The dependences of transition probabilities on N′ were obtained for the first time for the first four diagonal bands of the r ³Π _g ⁻, s ³Δ _g ⁻ → c ³Π _u ^± transitions. Original Russian Text ? S.A. Astashkevich, B.P. Lavrov, A.V. Modin, I.S. Umrikhin, 2008, published in Khimicheskaya Fizika, 2008, Vol. 27, No. 2, pp. 22–38.     

Nonadiabatic effects in the phonon spectra of superconductors

The nonadiabatic corrections to the self-energy part Σ_s(q, ω) of the phonon Green’s function are studied for various values of the phonon vectors q resulting from electron-phonon interactions. It is shown that the long-range electron-electron Coulomb interaction has no direct influence on these effects, aside from a possible renormalization of the corresponding constants. The electronic response functions and Σ_s(q, ω) are calculated for arbitrary vectors qand energy ω in the BCS approximation. The results obtained for q=0 agree with previously obtained results. It is shown that for large wave numbers q, vertex corrections are negligible and Σ_s(q, ω) possesses a logarithmic singularity at ω=2Δ, where Δ is the superconducting gap. It is also shown that in systems with nesting, Σ_s(Q, ω) (where Q is the nesting vector) possesses a square-root singularity at ω=2Δ, i.e., exactly of the same type as at q=0. The results are used to explain the recently published experimental data on phonon anomalies, observed in nickel borocarbides in the superconducting state, at large q. It is shown, specifically, that in these systems nesting must be taken into account in order to account for the emergence of a narrow additional line in the phonon spectral function S(q, ω)≈−π ⁻¹ Im D _s (q, ω), where D _s (q, ω) is the phonon Green’s function, at temperatures T<T _c . Zh. éksp. Teor. Fiz. 115, 1799–1817 (May 1999)     

Perturbations in the rotational structure of the 4<Emphasis Type="Italic">p</Emphasis> complex of H<Subscript>2</Subscript> molecule terms

A statistical analysis of all the available data on the wave numbers of spectral lines related to triplet-triplet electronic-vibrational-rotational (rovibronic) radiation transitions into the H₂ molecule (1sσ2sσ) a ³Σ _g ⁺ electronic state was performed for the first time. This allowed us to check and refine the controversial identification of several spectral lines. Optimum rovibronic term values were found for 15 electronic states, including the (4pσ)f ³Σ _u ⁺, (4pπ)k ³Π _u ⁺, and (4pπ)k ³Π _u ⁻ states studied in this work. The ratios between the oscillator strengths of R- and P-branch lines with common upper levels (branching coefficients) for the f ³Σ _u ⁺ → a ³Σ _g ⁺ and k ³Π _u ⁺ → a ³Σ _g ⁺ systems of H₂ molecule bands were measured for the first time. Substantial deviations of the measured branching coefficients from the corresponding ratios between the Henl-London factors were observed. The deviations monotonically increased as the rotational quantum number N grew, which, in combination with substantial Λ-doubling in the k ³Π _u state, was evidence of an important role played by electronicrotational interaction in the 4pσ³Σ _u ⁺ and 4pπ³Π _u ⁺ adiabatic electronic states. A strong correlation was observed between the N dependences of branching coefficients for transitions from the mutually perturbed f ³Σ _u ⁺ and k ³Π _u ⁺ electronic states. The results of this work show that the measured branching coefficients are a much more sensitive and capacious channel of information about perturbation effects than rovibronic term values.     

Possible molecular states of D*s[`(D)]*sD^{*}_{s}\bar{D}^{*}_{s} system and Y(4140)

The interpretation of Y(4140) as a D^*_s[`(D)]<sup>*</sup><sub>s</sub>D^{*}_{s}\bar{D}^{*}_{s} molecule is studied dynamically in the one boson exchange approach, where σ, η and φ exchange are included. Ten allowed D<sup>*</sup><sub>s</sub>[`(D)]^*_sD^{*}_{s}\bar{D}^{*}_{s} states with low spin parity are considered, and we find that the J ^PC =0⁺⁺, 1⁺⁻, 0⁻⁺, 2⁺⁺ and 1⁻⁻ D^*_s[`(D)]<sup>*</sup><sub>s</sub>D^{*}_{s}\bar{D}^{*}_{s} configurations are most tightly bound. We suggest that the most favorable quantum numbers are J <sup>PC</sup> =0<sup>++</sup> for Y(4140) as a D<sup>*</sup><sub>s</sub>[`(D)]^*_sD^{*}_{s}\bar{D}^{*}_{s} molecule; however, J ^PC =0⁻⁺ and 2⁺⁺ cannot be excluded. We propose to search for the 1⁺⁻ and 1⁻⁻ partners in the J/ψ η and J/ψ η′ final states, which is an important test of the molecular hypothesis of Y(4140) and the reasonability of our model. The 0⁺⁺ B^*_s[`(B)]^*_sB^{*}_{s}\bar{B}^{*}_{s} molecule should be deeply bound; experimental search in the ϒ(1S)φ channel at Tevatron and LHC is suggested.     

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

New results from the HAPPEX Experiments at Q<Superscript>2</Superscript> = 0.1GeV/c<Superscript>2</Superscript>

The nucleon's strange electric and magnetic form factors G _E ^s and G _M ^s can be probed via parity-violating electron scattering. The HAPPEX Collaboration has made new measurements of the parity-violating asymmetry A _PV in elastic scattering of 3GeV electrons off hydrogen and ⁴He targets with 〈θ_lab〉 ≈ 6.0^° . For ⁴He the preliminary result is A _PV = (+ 6.43±0.23(stat)±0.22(syst))×10^-6 . For hydrogen the preliminary result is A _PV = (- 1.60±0.12(stat)±0.05(syst))×10^-6 . From these values we extract G ^s _E = 0.004±0.014±0.013 at 〈Q ²〉 = 0.077 GeV/c^2 , and G ^s _E +0.09G ^s _M = 0.004±0.011±0.005 at 〈Q ²〉 = 0.109 GeV/c^2 , both consistent with zero, providing stringent new limits on the role of strange quarks in the vector structure of the nucleon.     

Application of Boltzmann Equation on Spin Diffusion of Ferromagnetic Superfluid <Superscript>3</Superscript>He: Near Critical Temperature

Different scattering processes of quasiparticles containing a binary process, a coalescence process and a decay process in transition probabilities are taken into account. In the meantime, interaction between Bogoliubov quasiparticles as well as that between normal and superfluid components (spin up-spin down quasiparticles) of ferromagnetic superfluid ³He-A ₁ are considered. Pfitzner procedure is used in the calculation of triplet and singlet quasiparticle scattering amplitude existing in transition probabilities of the collision integral of standard Boltzmann equation at melting pressure. Pfitzner procedure is extended beyond s-p approximation by adding higher angular momentum components. Then, using the results of Boltzmann equation and considering smallness of the gap close to T _c↑, the change of the spin diffusion coefficients tensor of the A ₁-phase of superfluid ³He close to critical temperature and melting pressure is calculated. Temperature dependence of the spin diffusion coefficient change, i.e., δD _xyxy /D⌈=(3/2)(δD _xzxz /D)⌉, is −0.71(1−(T/T _c↑))^1/2. It is also shown that interaction between normal and Bogoliubov quasiparticles (normal-superfluid components interaction) is very important to transport properties such as spin diffusion close to critical temperature. Furthermore, using s-p approximation, the prefactor of δD _xyxy /D is plotted in terms of pressure; hence, the pressure dependence of δD _xyxy /D is also determined.