Influence of local excitation of octupolar Oligophenylenevinylenes on their dipole moments

Absorption and fluorescence spectra of octupolar centrosymmetric oligophenylenevinylene dyes (E,E)-bis[2-(4-hexyloxyphenyl)ethenyl]-(E,E)-3,6-bis-[2-(4-N,N-dipropylaminophenyl)ethenyl]pyrazine and (E,E,E,E)-2,3,5,6- tetra-[2-(4-hexyloxyphenyl)ethenyl]pyrazine were measured in various solvents. An electro-optical absorption method was used to determine their dipole moments as μ _g  = 6.1∙10^–30 and 3.4∙10^–30 C∙m in the equilibrium ground state and the increased values ∆ ^a μ = 11.9∙10^–30 and 8.2∙10^–30 C∙m upon excitation into a Franck–Condon state. Quantum-chemical calculations showed that the molecules had non-planar configurations. The π,π-conjugated system was localized on the most planar part of the molecule that was responsible for light absorption in the range 300–450 nm due to a change in the geometry of the molecules in the ground state. Localized excitation of the molecules caused their dipole moments ∆ ^a μ to change significantly.     

Stilbene-Like Molecules as Fluorescent Probes Applied for Monitoring of Polymerization Process

2-(p-N,N-dimethylaminostyryl)benzoxazole (OS), 2-(p-N,N-dimethylaminostyryl)-benzothiazole (SS) and 2-(p-N,N-dimethylaminostyryl)naphtiazole (PS) were prepared and their absorption and fluorescence spectra were measured in various solvents at room temperature. On the basis of the solvatochromic behavior the ground state (μ_g) and excited state (μ_e) dipole moments of these pN,N-dimethylaminostyryl derivatives were evaluated. The dipole moments (μ_g and μ_e) were estimated from solvatochromic shifts of absorption and fluorescence spectra as function of the dielectric constant (ɛ) and refractive index (n) of applied solvents. The absorption spectra only slightly are affected by the solvent polarity in contrast to the fluorescence spectra that are highly solvatochromic and display a large Stokes shift. The analysis of the solvatochromic behavior of the fluorescence spectra as function of Δf (ɛ, n) revealed that the emission occurs from a high polarity excited state. The large dipole moment change along with the strongly red-shifted fluorescence, as the solvent polarity is increased, demonstrate the formation of an intramolecular charge transfer state (ICT). Compounds under the study were used as fluorescence probes for monitoring the kinetics of polymerization. The study on the changes in fluorescence intensity and spectroscopic shifts of studied compounds were carried out during thermally initiated polymerization of methyl methacrylate (MMA) and during photoinitiated polymerization of 2-ethyl-2-(hydroxymethyl)propane-1,3-diol triacrylate (TMPTA).     

Gemma experiment: Three years of the search for the neutrino magnetic moment

The result of the 3-year neutrino magnetic moment measurement at the Kalinin Nuclear Power Plant (KNPP) with the GEMMA spectrometer is presented. Antineutrino-electron scattering is investigated. A high-purity germanium detector of 1.5 kg placed at a distance of 13.9 m from the 3 GW_th reactor core is exposed to the antineutrino flux of 2.7 × 10¹³ cm⁻² s⁻¹. The scattered electron spectra taken in (5184 + 6798) and (1853 + 1021) h for the reactor ON and OFF periods are compared. The upper limit for the neutrino magnetic moment μ_v < 3.2 × 10⁻¹¹μ _B at 90% CL is derived from the data processing.     

Re-appraisal of the <Emphasis Type="Italic">P,T</Emphasis>-odd interaction constant <Emphasis Type="Italic">W</Emphasis><Subscript>d</Subscript> in YbF: Relativistic configuration interaction approach

Restricted active space (RAS) configuration interaction (CI) approach is employed to compute the P,T-odd interaction constant W _d for the ground (²Σ_1/2) state of YbF molecule. The present estimate of W _d = −1.164 × 10²⁵ Hz/e-cm is expected to provide a reliable limit on the electron’s electric dipole moment (EDM), d _e.     

Kinetics of processes in the middle atmosphere during the laser excitation of O2 molecules

Kinetic processes taking place in the atomic-molecular system O-O₂-O₃ in the middle atmosphere with the participation of oxygen molecules in the excited electronic states O₂(a ¹Δ_g) and O₂(b ¹Σ _g ⁺ ) are analyzed in detail. The possibility of increased ozone production under the influence of solar radiation during the laser excitation of O₂ molecules in the a ¹Δ_g state is demonstrated on the basis of numerical modeling. Upper and lower bounds are determined for the densities of O₂(a ¹Δ_g) molecules at which the ozone concentration increases in the irradiated zone. Zh. Tekh. Fiz. 68, 15–23 (August 1998)     

Measurement of the Magnetic Moment of the First Excited State in 93Sr Using on-line TDPAC technique

The g-factor of the first excited state of ⁹³Sr (E = 213 keV, T _1/2 = 4.6 ns) was measured by an on-line TDPAC technique with use of the strong hyperfine field in Fe metal. The Larmor frequency ω _L = (2.60 ± 0.15) × 10⁸ rad/s was obtained. The g-factor is derived as g = −0.227 ± 0.013 from g = −ℏω _L/B _hf μ _N. If the spin of the first excited state of ⁹³Sr is assumed to be 3/2, the g-factor is predicted by a simple core-excitation model as g = −0.22, which is in good agreement with the present experimental result.     

Solvent Effect on Absorption and Fluorescence Spectra of Three Biologically Active Carboxamides (C<Subscript>1</Subscript>, C<Subscript>2</Subscript> and C<Subscript>3</Subscript>). Estimation of Ground and Excited State Dipole Moment from Solvatochromic Method Using Solvent Polarity Parameters

The absorption and fluorescence spectra of three Carboxamides namely (E)-2-(4-Chlorobenzylideneamino)-N-(2-chlorophenyl)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₁), (E)-N-(3-Chlorophenyl)-2-(3, 4-dimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₂) and (E)-N-(3-Chlorophenyl)-2-(3, 4, 5-trimethoxybenzylideneamino)-4, 5, 6, 7-tetrahydrobenzo[b]thiophene-3-carboxamide (C₃) have been recorded at room temperature in solvents of different polarities using dielectric constant (ε) and refractive index (n). Experimental ground (μ_g) and excited (μ_e) state dipole moments are estimated by means of solvatochromic shift method and also the excited dipole moments are estimated in combination with ground state dipole moments. It was estimated that dipole moments of the excited state were higher than those of the ground state of all three molecules. Further, the changes in dipole moment (Dm \Delta \mu ) were calculated both from solvatochromic shift method and on the basis of microscopic empirical solvent polarity parameter (E_T^N E_T^N ) and the values are compared.     

A Fe<Superscript>3+</Superscript>/Hg<Superscript>2+</Superscript>-Selective Anthracene-Based Fluorescent PET Sensor with Tridentate Ionophore of Amide/β-Amino Alcohol

A new anthracene-based fluorescent PET sensor 1 with a tridentate ionophore of amide/β-amino alcohol displays very good selectivity and sensitivity for Fe³⁺ (K _a = 1.6 × 10³ M⁻¹) and Hg²⁺ (K _a = 2.1 × 10³ M⁻¹) in CH₃CN–H₂O (3:7, v/v) with detection limit of 1 μM. More fluorescence enhancement was observed when 1 selectively detected Fe³⁺ or Hg²⁺ in CH₃CN and its detection limit was up to 0.03 μM.     

Dipole Moments of 4′-Aminoflavonol Fluorescent Probes in Different Solvents

Electrooptical absorption measurements (EOAM) were used to measure the dipole moments of the normal form of 4-(dimethylamino)-3-hydroxyflavone (FME), and 4 N-(15-azacrown-5)-3-hydroxyflavone (FCR) in 1,4-dioxane, toluene, and cyclohexane. With these probes excited-state intramolecular proton transfer (ESIPT) takes place. For comparison, the dipole moments of 4-(dimethylamino)-3-metoxyflavone (FME3ME), for which ESIPT is lacking, were measured, too. For all three probes the ground (_g) and excited Franck-Condon state (_e^FC) electrical dipole moments are parallel to each other and also parallel to the transition dipole moment. The electrical dipole moments of FCR, FME, and FME3ME in their ground state have values within the range (12.0–17.7) × 10^–30 C m. Upon optical excitation, the dipole moments increase by (41.9–52.9) ×10^–30 C m. The value of the change of the dipole moment vector ^a with excitation to the Franck-Condon state and the value of the vector _e^FC for FCR and FME are practically independent on the solvent polarity. From this point of view and due to large values of the dipole moments FCR and FME are very promising probes for the investigation of the distribution of the local polarity in biological systems using site-selective excitation of the different sites. Our steady-state fluorescence studies on FME and FCR have demonstrated a high spectral sensitivity of the normal form to such solvent characteristics as polarity.     

Universal relation between spectroscopic constants

A universal relation between the Sutherland parameter, Δ (= k _e r _e ^/2 /2D _e) and the dimensionless parameter G (= 8ω _e x _e /B _e ), has been established using 40 electronic states, which include ground as well as excited states of polar and non-polar molecules. This relation is used to predict the dissociation energy of four lowest electronic states of S ₂ molecule. The respective values for the states X ³Σ _g ^/− , a ¹Δ _g , b ¹Σ _g ^/+ and B ³Σ _u ^/− turn out to be 36557, 31431, 28247 and 13429 cm⁻¹, and are in good agreement with the experimental values. Furthermore, metastable states a ¹Δ _g and b ¹Σ _g ^/+ of S ₂ are shown to dissociate into ³ P ₁ + ³ P ₁ as against the dissociation of X ³Σ _g ^/− into ³ P ₂ + ³ P ₁. In addition, a relation between Sutherland parameter Δ and internuclear distance r _e , viz., Δ=2.2r _e has been obtained for the ground state of alkali diatomic molecules.     

Solvatochromic Effect on the Photophysical Properties of Two Coumarins

The absorption and emission spectra of two coumarins namely 7, 8 benzo-4-azidomethyl coumarin (C₁) and 6-methoxy-4-azidomethyl coumarin (C₂) have been recorded at room temperature in solvents of different polarities. The ground state dipole moments (μ _g ) of two coumarins were determined experimentally by Guggenheim method. The exited state (μ _e ) dipole moments were estimated from Lippert’s, Bakhshievs and Chamma-Viallet’s equations by using the variation of Stoke’s shift with the solvent dielectric constant and refractive index. The ground and excited state dipole moments were calculated by means of solvatochromic shift method and also the excited state dipole moments are determined in combination with ground state dipole moments. It was observed that dipole moments of excited state were higher than those of the ground state, indicating a substantial redistribution of the π-electron densities in a more polar excited state for two coumarins.     

Contribution of semi-hadronic states <Emphasis Type="Italic">P</Emphasis>γ, <Emphasis Type="Italic">S</Emphasis>γ, π<Superscript>+</Superscript>π<Superscript>−</Superscript>γ to amm of muon in the framework of the Nambu-Jona-Lasinio model

We calculate the contribution of semi-hadronic states with the pseudoscalar P = π⁰, η and scalar (σ(550)) meson accompanied with a real photon as an intermediate state of a heavy photon to the anomalous magnetic moment of the muon. We consider the intermediate states with π⁰ and σ as hadrons in the frame-work of the Nambu-Jona-Lasinio (NJL) model. The contribution of the π⁰γ state is in agreement with results obtained in previous theoretical considerations as well as with the experimental data $ a_\mu ^{\pi _0 \gamma } \approx 4.5 \times 10^{ - 10} $ a_\mu ^{\pi _0 \gamma } \approx 4.5 \times 10^{ - 10} , besides we estimate a _μ^ηγ = 0.7 × 10⁻¹⁰, a _μ^σγ ∼ 1.5 × 10⁻¹¹, $ a_\mu ^{\pi ^ + \pi ^ - \gamma } \sim 3.2 \times 10^{ - 10} $ a_\mu ^{\pi ^ + \pi ^ - \gamma } \sim 3.2 \times 10^{ - 10} . We also discuss the light-by-light (LbL) mechanism with a _μ ^lbl = 10.5 × 10⁻¹⁰.     

EPR and Optical Study of Cu<Superscript>2+</Superscript> Ions Doped in Sodium Zinc Sulfate Tetrahydrate Single Crystals

Electron paramagnetic resonance (EPR) study of Cu²⁺-doped sodium zinc sulfate tetrahydrate is done at liquid nitrogen temperature. Two magnetically equivalent sites for Cu²⁺ are observed. The spin-Hamiltonian parameters determined by fitting the EPR spectra to the rhombic-symmetry crystalline field are g _x  = 2.2356, g _y  = 2.0267, g _z  = 2.3472, A _x  = 27 × 10⁻⁴ cm⁻¹, A _y  = 54 × 10⁻⁴ cm⁻¹and A _z  = 88 × 10⁻⁴ cm⁻¹. The ground state wave function is also determined. The g-anisotropy is evaluated and compared with the experimental value. With the help of optical study, the nature of bonding in the complex is discussed.     

Mott-insulator-superfluid-liquid transition in a one-dimensional bosonic Hubbard model: Quantum Monte Carlo method

The values of the insulator gap Δ in one-dimensional systems of interacting bosons described by the Hubbard Hamiltonian are calculated at low temperatures by the quantum world-line Monte Carlo algorithm. The dependence of Δ on the size of the system, the temperature, and the parameters of the model is investigated. It is shown that a chain with N _a=50 sites is already sufficient to estimate the thermodynamic value of the critical quantity (t/U)_c for which a transition from the insulator into the superfluid state occurs in a commensurate system. To within the computational error, this value, (t/U)_c=0.300±0.005, agrees with the value (t/U)_c=0.304±0.002 obtained previously by the combined “exact diagonalization + renormalization-group analysis” method. The characteristic Kosterlitz-Thouless behavior of the insulator gap is demonstrated near the critical region: Δ∼exp[−b(1−t/t _c)^−1/2]. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 2, 92–96 (25 July 1996)     

Singlet molecular nitrogen in the Auroral ionosphere and under the conditions of laboratory discharge

Using the suggested model of the electron kinetics of N₂ singlet states, the population of the vibrational levels in the molecular nitrogen states (a′)¹Σ _u ⁻, a ¹Π _g , and w ¹Δ _u is calculated for the case when fast auroral electrons penetrate into the Earth’s ionosphere. It is shown for the first time that the population distribution of the vibrational levels v = 0−6 in the state a ¹Π _g in the auroral ionosphere and also in a laboratory discharge varies with atmospheric pressure insignificantly. Similar calculations for pure nitrogen atmosphere show a considerable increase in the populations of lower vibrational levels (v = 0−2) with rising pressure.     

Doppler-free optical double resonance spectroscopy using a single-frequency laser and modulation sidebands

Principles and applications are described for a form of Doppler-free optical double resonance spectroscopy which uses amplitude modulation sidebands (v _L ±v) imposed on a single laser frequency (v _L ). The sidebands are generated by passing the carrier radiationv _L through an electro-optic modulator, driven at a radiofrequency ν, which enables the intensity and polarization characteristics of the emerging radiation to be varied for enhancement of selected double-resonance processes. The technique has been applied to infrared-infrared double-resonance studies of the Stark effects of a variety of molecules—¹³CH₃F,¹²CH₃F, PH₃,¹⁵NH₃, GeH₄, SiH₄, and CH₃D—for which physical results are presented and discussed. These results include determination of extremely small electric dipole moments (10⁻³–10⁻⁵ debye) for GeH₄ and CH₃D and, for the dipole moment of PH₃, a vibrational state dependence which is extremely small (Δμ=0.0028(5) debye for ∣Δv ₂∣=1) and a rotational state dependence which is of an unexpected sign. The spectra recorded in some cases display unusual polarization and optical saturation effects which deviate markedly from the predictions of a simple three-wave polarization theory.     

Subnanosecond spectrofluorimetry of new indolocarbazole derivatives in solutions and protein complexes and their dipole moments

The spectral and temporal characteristics of new 6,12-dimethoxyindolo[3,2-b]carbazole, 5,11-dimethyl-6,12-dimethoxyindolo[3,2-b]carbazole, and 5,11-dihexyl-6,12-di(hexyloxy)indolo[3,2-b]carbazole fluorescence probes in organic solvents and protein complexes are studied. The dipole moments of indolocarbazoles in 1,4-dioxane were measured by electrooptical absorption method. The measured dipole moments have values within the range of (3.1–3.6) × 10⁻³⁰ C m in the equilibrium ground state and increase to (4.8–5.6) × 10⁻³⁰ C m after excitation. The excited state lifetime of indolocarbazole derivatives increases with increasing polarity and viscosity of the environment. The binding of indolocarbazoles with trypsinogen and human serum albumin increases the fluorescence intensity, changes the intensity ratio of fluorescence bands, and increases the average excited state lifetime of indolocarbazoles. The analysis of the instantaneous fluorescence spectra and fluorescence decay parameters at different wavelengths revealed the existence of several types of probe binding sites in proteins. It is found that the fluorescence characteristics of indolocarbazole derivatives depend on the conformation rearrangements of trypsinogen due to its thermal denaturation.     

EPR and Optical Absorption Studies of Cu2+-Doped Bis(l-Asparaginato)Mg(II)

The electron paramagnetic resonance study of Cu²⁺-doped bis(l-asparaginato)Mg(II) is performed at room temperature. Two magnetically non-equivalent sites for Cu²⁺ are observed. The spin-Hamiltonian parameters evaluated by fitting spectra to the crystalline field of rhombic symmetry are as follows: g _x  = 2.0420 ± 0.0002, g _y  = 2.0808 ± 0.0002, g _z  = 2.3600 ± 0.0002, A _x  = (99 ± 2) × 10⁻⁴ cm⁻¹, A _y  = (108 ± 2) × 10⁻⁴ cm⁻¹, A _z  = (140 ± 2) × 10⁻⁴ cm⁻¹. The ground state wave function of Cu²⁺ is also determined. The g-anisotropy is estimated and compared with the experimental value. Further, with the help of optical study the nature of bonding of a metal ion with different ligands in the complex is discussed.     

Probability of the occurrence of freak waves

The statistics of the occurrence of freak waves on a surface of an ideal heavy liquid is studied. The freak (rogue, extreme) waves arise in the course of evolution of a statistically homogeneous random Gaussian wave field. The mean steepness of initial data varies from small (μ² = 1.54 × 10⁻³) to moderate (μ² = 3.08 × 10⁻³) values. The frequency of the occurrence of extreme waves decreases with an increase in the spectral width of the initial distribution, but remains relatively high even for broad spectra (Δ _k /Δ ∼ 1).     

Structure perfection of single-crystal quartz intended for experiments on finding the electrical dipole moment of neutrons by the crystal diffraction method

The perfection of quartz crystals of different origins intended for experiments on finding the electrical dipole moment of neutrons is studied. The study is carried out using the crystal diffraction method by passing a neutron through the crystal under near-Bragg conditions at a diffraction angle of about 90°. It is shown that optical-grade quartz grown at the All-Russia Research Institute for Synthesis of Mineral Raw Materials (VNIISIMS, Aleksandrov, Vladimir oblast) offers the highest perfection and homogeneity. Of a total of 22 crystals, 15 best ones with a spread in the interplanar distance of Δd/d ₀ ≤ 5 × 10⁻⁶ were selected for experiments. The crystals measure 100 × 100 × 500 mm.