Molecular thermometers based on phosphorescent porphin metal complexes

We study the temperature dependence of the radiative deactivation of triplet states of Pdand Pt-porphin molecules in n-alkane matrices in the temperature range 4.2–210 K. The nature of the thermally activated “hot” lines that are observed in phosphorescence spectra of Pdand Pt-porphin is discussed in detail. We show that, because of the degeneracy lifting of the triplet state T _{1, 2} in the crystal field of n-alkane matrices, lines of the transitions T1 → S ₀ and T ₂ → S ₀ are spectrally spaced and, in all cases, the T ₂ state is the first state that is activated with increasing temperature. We analyze the dependences of the T ₂-T ₁ splitting on the chelated metal ion and the type of the matrix. The possibility of measuring cryogenic temperatures with molecular thermometers that use the thermochromic properties of Pdand Pt-porphin in n-alkane matrices is discussed.     

Spectral characteristics of heterocyclic compounds with a chain structure, cooled in an ultrasonic jet

We have recorded the fluorescence excitation spectra of three heterocyclic compounds with a chain structure [BPO (2-phenyl-5-(4-diphenylyl)oxazole), POPOP (1,4-di[2-(5-phenyloxazolyl)]benzene, and TOPOT (1,4-di[2-(5-n-tolyloxazolyl)]benzene] and the fluorescence spectra of POPOP, under conditions where the molecules were cooled in an ultrasonic helium jet. A line structure is observed in the spectra of POPOP and TOPOT; for the BPO molecules, whose configuration changes considerably during electronic excitation, vibrational structure is apparent only in the low-frequency region of the excitation spectrum, and a diffuse spectrum is recorded starting from ν ₀ ⁰ + 200 cm⁻¹. For all the compounds, in the spectra we recorded vibrations with frequencies up to 100 cm⁻¹, arising due to the flexibility of the molecular structure. The rotational contours of the lines for the electronic and vibronic transitions of the POPOP molecules (T_rot = 10.5 K) and TOPOT molecules (T_rot = 15 K) are structureless and bell-shaped. The degree of polarization of the fluorescence P_fl for the jet-cooled POPOP molecules for excitation of vibrations along the absorption band up to 2000 cm⁻¹ above ν ₀ ⁰ is practically constant (∼8.4%) and matches P_fl for high-temperature vapors. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 728–734, November–December, 2006.     

Formation of SERS-active silver structures on the surface of mesoporous silicon

We have optimized the procedure for preparation of nanostructured silver films on the surface of mesoporous silicon (PSi) to use them as active substrates in surface-enhanced Raman scattering (SERS) spectroscopy. The greatest enhancement of the SERS signal was observed for samples obtained when the silver was deposited on PSi from an aqueous AgNO₃ solution with concentration 1⋅10^–2 M over a 10–15 minute period. The detection limit for rhodamine 6G on SERS-active substrates prepared by the optimized procedure was 1⋅10^–10 M. The enhancement factor for the SERS signal on these surfaces was estimated as ≈2⋅10⁸. We have shown that SERS-active substrates based on mesoporous silicon are promising for detection and study of complex organic compounds, in particular tetrapyrrole molecules. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 2, pp. 298–306, March–April, 2009.     

Optical properties of new organic conductors based on the BEDT-TSeF molecule (the κ-(BETS)4Hg2.84Br8 superconductor and κ-(BETS)4Hg3Cl8 Metal) in the range 300–15 K

Polarized reflectance and optical conductivity spectra of single crystals of two new isostructural organic conductors based on the BEDT-TSeF molecule, namely, the κ-(BETS)₄Hg_2.84Br₈ superconductor (T _c =2 K) and the κ-(BETS)₄Hg₃Cl₈ metal, which undergoes a smooth transition to the dielectric state near 35 K, have been obtained in the spectral region 700–6500 cm⁻¹ at temperatures of 300–15 K. At 300 K, the spectra of both compounds are nearly identical and differ from the Drude spectrum characteristic of metals. The nature of the observed difference is discussed, and the spectra are described in terms of a cluster approach with inclusion of electron-electron correlations in the Hubbard approximation combined with the Drude model. The parameters of the theory were determined, including the electron transfer integrals between molecules in a cluster. The spectra in the conducting plane of the crystals were found to be essentially anisotropic, which should be assigned to specific features of in-plane interaction between molecules. The spectra of the superconductor and the metal become increasingly different as the temperature is lowered. The spectra of the metal obtained for T<150 K exhibit splitting of the broad electronic maximum in the mid-IR region into two bands, which is accompanied by a splitting of a vibronic feature deriving from electron interaction with intramolecular BETS vibrations of ν₃(A _g ) symmetry. No such splitting is observed in the superconductor spectra with decreasing temperature. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 11, 2004, pp. 1921–1929. Original Russian Text Copyright ? 2004 by Vlasova, Drichko, Petrov, Semkin, Zhilyaeva, Lyubovskaya, Olejniczak, A. Kobayashi, H. Kobayashi.     

Absorption,fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives

We have obtained and analyzed the absorption, fluorescence, and fluorescence excitation spectra of indole vapor, N-acetyl-L-tryptophan vapor, and 3-indole aldehyde vapor. From analysis of the dependence of the fluorescence spectrum of the free indole molecules on the wavelength of the exciting radiation λ_ex, it follows that emission of fluorescence occurs when the molecules undergo a transition from the one electronically excited state ¹L_b. The fluorescence spectra of the studied compounds are insignificantly different, suggesting a major role for the indole chromophore in formation of the compounds. The absorption spectrum of N-acetyl-L-tryptophan, in which the group of atoms is added to the indole ring through a-C-C bond, is similar to the spectrum of indole, while the spectrum of 3-indole aldehyde is significantly different from the indole spectrum due to the effect of the C=O group conjugated with the indole ring. The fluorescence excitation spectra are considerably different from the absorption spectra. This is associated with the strong dependence of the quantum yield for the free molecules on λ_ex. Qualitatively, they are mirror-symmetric to the fluorescence spectra of the stodied compounds. Analysis of the data obtained provides a basis for assuming that in the case of free molecules of indole and its derivatives, the ¹L_a absorption in the extreme long-wavelength region of the spectrum does not overlap ¹L_b absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 218–222, March–April, 2007.     

Optical properties of new indotricarbocyanine dye as a limiter of laser radiation power

We present results of experimental and theoretical studies of the optical characteristics of a new indotricarbocyanine dye that is capable of effectively limiting the power of laser radiation in the visible spectral range. The spectral-luminescent and energy characteristics of the dye molecules and their absorption spectra from the excited state with nanosecond resolution are investigated experimentally. Quantum-chemical methods are used to calculate electronic absorption spectra from the ground (S₀ → S_n) and excited (S₁ → S_n) states and to determine the nature of electronic states of the molecule and the rate constants of intramolecular photophysical processes. The results of the theoretical research agree with experimental data. It is shown that the investigated dye has singlet-singlet absorption at 400–600 nm. Nonlinear absorption of the dye upon excitation by radiation of the second harmonic of a Nd:YAG laser is studied by z-scanning with an open diaphragm. The ratio of dye absorption cross sections from the excited and ground states at 532 nm is determined in the framework of a three-level model. The results are compared with those for previously studied compounds. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 473–480, July–August, 2007.     

Paramagnetic and spin-glass properties of pyrochlore-like oxides Ln2Mn2/3Mo4/3O7 (Ln=Sm, Gd, Tb, or Y)

The magnetic properties of complex oxides Ln ₂Mn_2/3Mo_4/3O₇ (Ln=Sm, Gd, Tb, or Y) with a pyrochlore-type structure are studied in the temperature range 2–300 K. For all compounds in the paramagnetic state, the temperature dependence of the magnetic susceptibility is described by a generalized Curie-Weiss law with a temperature-independent component of ∼10⁻⁶ cm³/g and with a Weiss constant Θ<0 and |Θ|<16 K. At low temperatures (T<10–12 K), the compounds have spin-glass properties; they exhibit magnetic and temperature hysteresis and the typical dependences of the imaginary and real parts of the dynamic magnetic susceptibility on temperature and the frequency of an ac magnetic field in a wide range of magnetization relaxation times. The data obtained suggest that d electrons are responsible for the formation of frustrated exchange interactions in the compounds and that 4f electrons in the compounds with Sm or Tb provide strong magnetic-anisotropy effects. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 2, 2004, pp. 287–295. Original Russian Text Copyright ? 2004 by Korolev, Bazuev.     

Luminescence of CaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>:Eu crystals

We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa₂Se₄:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f⁶ 5d–4f⁷ (⁸S_7/2) of the Eu²⁺ ions. From the temperature dependence of the intensity (log I–10³/T), we determined the activation energy (E _a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu²⁺ ions in the CaGa₂Se₄ crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.     

Probability estimate for intersystem crossings in naphthalene and acenaphthene in the presence of benzophenone

To a first approximation in perturbation theory, we have obtained expressions for the rate constants for intersystem crossings in acceptor molecules. We show that exchange interactions between the components of the donor-acceptor pair can change the probability of intersystem crossings for both radiative T → S₀ and nonradiative S₁ → T transitions. The theoretical conclusions are supported by the results of experimental studies. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 550–553, July–August, 2006.     

A Two-Dimensional Relaxation Study of the Evolving Microstructure in a Mixed Biopolymer Gel

It is shown that two-dimensional (2-D) T ₁–T ₂ relaxation spectra are sensitive to the changing microstructure in a model food system comprising water-in-water gelatin–agarose gelled emulsions. This 2-D relaxation–microstructure relationship suggests that T ₁–T ₂ spectra have the potential of acting as “fingerprint” molecular biomarkers of microstructure in complex water-rich biological systems and this has important future implications for in vivo magnetic resonance imaging studies of food digestion and of the changing structure of cancerous tissue.     

Calorimetric study of phase transitions in the perovskite BaCeO3

Differential scanning calorimetry was used to study phase transitions (PT) in the perovskite BaCeO₃. It is shown that its phase state is determined by a second-order λ transition at T _tr=520–540 K and a first-order δ transition at T _tr=600–670 K. Differences in PT parameters between ceramic and fused BaCeO₃ have been established. Fiz. Tverd. Tela (St. Petersburg) 40, 2109–2112 (November 1998)     

Electronic structure of linear chains of fullerenes

The band structure of linear chains of fullerene molecules is calculated as a function of the intermolecular π-electron overlap integral T, which increases under increasing external pressure. Chains consisting of neutral (C₆₀) and charged (C ₆₀ ⁻ ) molecules are studied. It is shown that there is a sharp transition from a metal (or narrow-gap semiconductor) to an insulator (with band gap ∼1 eV)with increasing T. The proposed model makes it possible to describe the formation of solid-carbon struc-tures, containing chains of covalently bound fullerene molecules, with different pressure-dependent semiconductor properties. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 647–650 (25 April 1997)     

Peculiarities of crystal field effects in CeInCu2 based heavy-fermion compounds

We have studied the evolution of the inelastic neutron magnetic scattering spectra of a compound with cubic symmetry, CeInCu₂, in the temperature range 10–130 K, and also their transformation with variation of the Kondo temperature T _K due to substitution of cerium ions in the system Ce_1−x (La,Y)_xInCu₂ at T=10 K. It turns out that the energy of the transition between the ground state and excited state of the 4 f electrons (Δ_CF) in the crystal electric field in CeInCu₂ increases with growth of the population of the ground state as the temperature is reduced, with a slight change in its intensity. Such behavior is inconsistent with the notion of classical one-ion effects of the crystal electric field. We have found that the scale of the observed variations in the excitation spectra of the 4f electrons depends on the Kondo temperature T _K and is insensitive to disorder in the rare-earth sublattice. Thus, despite the fact that T _K ≪Δ_CF, hybridization with states in the conduction band has a substantial effect on all parameters of the excitation spectrum of the ground multiplet of the 4f electrons at low temperatures. Zh. éksp. Teor. Fiz. 115, 2197–2206 (June 1999) A. A. Baikov Institute of Metallurgy     

A Generic C1 Expanding Map¶has a Singular S–R–B Measure

We show that for a generic C¹ expanding map T of the unit circle, there is a unique equilibrium state for − log T′ that is an S–R–B measure for T, and whose statistical basin of attraction has Lebesgue measure 1. We also present some results related to the question of whether a generic C¹ expanding map preserves a σ-finite measure, absolutely continuous with respect to Lebesgue measure. Received: 8 December 2000 / Accepted: 27 March 2001     

Magnetic properties of electron-irradiated quasi-layered manganites La2?2xSr1+2xMn2O7 (x=0.3, 0.35, 0.4)

The magnetic properties of La_2−2x Sr_1+2x Mn₂O₇ polycrystals (x=0.3–0.4) are studied over a broad temperature range 80–600 K. Quasi-two-dimensional manganites have a complex magnetic structure that undergoes several transitions from one type of magnetic ordering to another. A specific feature of these manganites is a hyperbolic dependence of inverse susceptibility in the transition region from the magnetically ordered to paramagnetic state for T>360 K. This suggests the onset of ferrimagnetism. Electron irradiation to a fluence Φ=1×10¹⁸ electrons/cm² is shown to have no effect on the long-range magnetic order while favoring the formation of paramagnetic polarons and of an inhomogeneous paramagnetic state. __________ Translated from Fizika Tverdogo Tela, Vol. 45, No. 8, 2003, pp. 1440–1445. Original Russian Text Copyright ? 2003 by Arbuzova, Naumov, Arbuzov.     

Influence of temperature on phosphorescence spectra of Pd-porphine in Shpol’skii matrices

We have studied the temperature dependence of the radiative deactivation of the Pd-porphine triplet states in Shpol’skii matrices in the temperature range 1.2–210 K. A substantial transformation of the phosphorescence spectra is observed as the temperature increases and is due to the inclusion of thermally activated Pd-porphine states in the radiative deactivation processes. The activation energy E_a of these Pd-porphine states is measured in matrices of n-octane and n-nonane. The splitting of the lowest quasidegenerate triplet state ΔE(T₂−T₁) is determined for planar and distorted conformations of the Pd-porphine macrocycle in the n-octane matrix as 40 and 57 cm⁻¹, respectively. The ability to use the temperature dependence of the phosphorescence properties of Pd-porphine to fabricate molecular thermometers for the low-temperature range is analyzed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 460–464, July–August, 2007.     

Characteristic features of vortex depinning in a layered superconductor

The field H*(T) for the onset of dissipation is estimated self-consistently from the results of an investigation of the transverse resistance and current-voltage characteristics of a Bi₂Sr₂CaCu₂O₈ (BSCCO-2212) single crystal in a mixed state. It is established that H* is close to H _c1 in the interval T _c/2⩽T⩽T _c. Rapid growth of H*(T), accompanied by a transformation of the current-voltage characteristics, as the temperature decreases below ≈ 40 K attests to the formation of a nonvanishing region of stability of an ordered state of the vortex system, possibly as a result of a change in the effective dimensionality of the fluxoid. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 629–634 (25 April 1997)     

Anomalous absorption in H<Subscript>2</Subscript>CN and CH<Subscript>2</Subscript>CN molecules

Structures of H₂CN and CH₂CN molecules are similar to that of H₂CO molecule. The H₂CO has shown anomalous absorption for its transition 1₁₁–1₁₀ at 4.8 GHz in a number of cool molecular clouds. Though the molecules H₂CN and CH₂CN have been identified in TMC-1 and Sgr B2 through some transitions in ortho as well as in para species, here we have investigated the condition under which transitions 1₁₁–1₁₀ and 2₁₂–2₁₁ of these molecules may show anomalous absorption. For the present investigation, we have calculated energy levels and radiative transition probabilities. However, we have used scaled values for collisional rate coefficients. We found that relative values of collisional rate coefficients can produce the required anom-alous absorption in 1₁₁–1₁₀ and 2₁₂–2₁₁ transitions in the molecules.      

On some liquid crystalline phases exhibited by compounds made of bent-core molecules and their mixtures with rod-like molecules

In most homologous series of compounds made of bent-core (BC) molecules, the B₂ B₁ and B₆ phases occur as the chain length decreases. We have studied binary mixtures of the compound 1,3-phenylene bis[4-(3-methylbenzoyloxy)]4-n-dodecylbiphenyl 4’-carboxylate (BC12) which exhibits the B₂ phase with the compound 4-biphenylyl 4’-n-undecyloxybenzoate (BO11) made of rod-like (R) molecules. We find the above sequence of occurrence of the B phases with increasing concentration of BOH. In this paper we describe the physical origin for the formation of these phases in both pure compounds and in the mixtures. We have also found the occurrence of the biaxial smectic A phase when the BO11 concentration is increased to 87–95.5 mol%. We also report on another binary system composed of BC12 and 4-n-octyloxy 4’- cyanobiphenyl (8OCB) made of R molecules. This system exhibits the biaxial smectic A phase down to 30°C. Using polarized infrared spectroscopy we find that the mutual orientation of the R and BC molecules in the SmA_db liquid crystal is such that the arrow axes of the BC molecules are along the layer normal of the partial bilayer smectic structure formed by the rods. We also describe unusual growth patterns obtained when the nematic phase transforms to the SmA_db phase in a mixture with 24 mol% of BC12.     

Equilibrium low temperature heat capacity of the spin density wave compound (TMTTF)<Subscript>2</Subscript>Br: effect of a magnetic field

We have investigated the effect of the magnetic field (B) on the very low-temperature equilibrium heat capacity c_eq of the quasi-1 D organic compound (TMTTF)₂Br, characterized by a commensurate Spin Density Wave (SDW) ground state. Below 1 K, c_eq is dominated by a Schottky-like A_ST^-2 contribution, very sensitive to the experimental time scale, a property that we have previously measured in numerous DW compounds. Under applied field (in the range 0.2–7 T), the equilibrium dynamics, and hence c_eq extracted from the time constant, increases enormously. For B ≥ 2–3 T, c_eq varies like B², in agreement with a magnetic Zeeman coupling. Another specific property, common to other Charge/Spin density wave (DW) compounds, is the occurrence of metastable branches in c_eq, induced at very low temperature by the field exceeding a critical value. These effects are discussed within a generalization to SDWs in a magnetic field of the available Larkin-Ovchinnikov local model of strong pinning. A limitation of the model when compared to experiments is pointed out.