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.     

Self-similar magnetic structures and magnetic flux “Giant” creep

The penetration of a magnetic flux into a type-II high-T _c superconductor occupying the half-space x > 0 is considered. At the superconductor surface, the magnetic field amplitude increases in accordance with the law b(0, t) = b ₀(1 + t)^m (in dimensionless coordinates), where m > 0. The velocity of penetration of vortices is determined in the regime of thermally activated magnetic flux flow: v = v ₀exp?ub;?(U _0/T )(1-b?b/?x)?ub;, where U ₀ is the effective pinning energy and T is the thermal energy of excited vortex filaments (or their bundles). magnetic flux “Giant” creep (for which U ₀/T? 1) is considered. The model Navier-Stokes equation is derived with nonlinear “viscosity” v ∝ U ₀/T and convection velocity v _f ∝ (1 ? U ₀/T). It is shown that motion of vortices is of the diffusion type for j → 0 (j is the current density). For finite current densities 0 < j < j _c, magnetic flux convection takes place, leading to an increase in the amplitude and depth of penetration of the magnetic field into the superconductor. It is shown that the solution to the model equation is finite at each instant (i.e., the magnetic flux penetrates to a finite depth). The penetration depth x _eff ^A (t) ∝ (1 + t)^{(1 + m/2)/2} of the magnetic field in the superconductor and the velocity of the wavefront, which increases linearly in exponent m, exponentially in temperature T, and decreases upon an increase in the effective pinning barrier, are determined. A distinguishing feature of the solutions is their self-similarity; i.e., dissipative magnetic structures emerging in the case of giant creep are invariant to transformations b(x, t) = β^m b(t/β, x/β^{(1 + m/2)/2}), where β > 0.     

Magnetized Quark-Gluon Plasma at the LHC

In QCD, the strengths of the large scale temperature dependent chromomagnetic, B₃, B₈, and usual magnetic, H fields spontaneously generated in quark-gluon plasma after the deconfinement phase transition (DPT), are estimated. The consistent at high temperature effective potential accounting for the oneloop plus daisy diagrams is used. The heavy ion collisions at the LHC and temperatures T not much higher than the phase transition temperature T_d are considered. The critical temperature for the magnetized plasma is found to be T_d (H) ～ 110–120 MeV. This is essentially lower compared to the zero field value T_d (H=0) ～ 160–180 MeV usually discussed in the literature. Due to contribution of quarks, the color magnetic fields act as the sources generating H. The strengths of the fields are B₃(T), B₈(T) ～ 10¹⁸–10¹⁹ G, H(T) ～ 10¹⁶–10¹⁷ G for temperatures T ～ 160–220 MeV. At temperatures T < 110–120 MeV the effective potential minimum value being negative approaches to zero. This is signaling the absence of the background fields and color confinement.     

Self-similar distribution in “giant” magnetic flux creep

The problem of magnetic field penetration into the half-space is considered in parallel geometry in an external magnetic field increasing with time in accordance with the law B(0, t, τ₀ = B _{c 1} (1 + t/τ₀) ^m , m ≥ 0, t ≥ 0 (τ ₀ is the time of magnetic flux redistribution and B _{c 1} is the lower critical field). It is assumed that the flow of vortices is thermally activated in the “giant” creep mode (i.e., for weak pinning creep and high temperatures). A model equation is derived for describing the magnetic flux evolution. Analytic formulas are obtained for the depth and velocity of magnetic field penetration. It is shown that the giant creep regime is stable for 0 ≤ m ≤ 1/2.     

Effect of the orbital structure and symmetry of electronic states on nonradiative <Emphasis Type="Italic">S-T</Emphasis> intersystem crossing: Dibenzofuran

The nonradiative S-T intersystem crossing S ₁(ππ*) ? T ₁(ππ*) in dibenzofuran (DB(O)) molecules has been theoretically investigated within the model of vibronically induced spin-orbit (VISO) coupling of electronic states, where the vibronic perturbation takes into account all out-of-plane vibrational modes of a molecule. It is established that the S-T intersystem crossing S ₁(¹ A ₁) ? T ₁(³ B ₂) involves also the intermediate (T _m )T ₂(³ A ₁) and T ₃(³ B ₂) triplet states. The calculated rate constant K _ST = (4.5–4.7) × 10⁷s^?1 of the nonradiative transition is in agreement with the known experimental data. The manifestation of approximate (belonging to the D _2h group) symmetry of singlet and triplet molecular states in VISO couplings has been studied. An effect of the heavy (oxygen) atom of a DB(O) molecule on K _ST is established.     

Self-gravitating Brownian particles in two dimensions: the case of N = 2 particles

We study the motion of N = 2 overdamped Brownianparticles in gravitational interaction in a space of dimensiond = 2. This is equivalent to the simplified motion of twobiological entities interacting via chemotaxis when time delay anddegradation of the chemical are ignored. This problem also bearssimilarities with the stochastic motion of two point vorticesin viscous hydrodynamics [O. Agullo, A. Verga, Phys. Rev. E 63,056304 (2001)]. We analytically obtain the probability density offinding the particles at a distance r from each other at timet. We also determine the probability that the particles havecoalesced and formed a Dirac peak at time t(i.e. the probability that the reduced particle has reached r = 0at time t). Finally, we investigate the meansquare separation \(\langle\) r ² \(\rangle\) and discuss the proper formof the virial theorem for this system. The reduced particle has anormal diffusion behavior for small times with a gravity-modifieddiffusion coefficient \(\langle\) r ² \(\rangle\) = r ₀ ² + (4k _B /ξ μ)(T–\(T_{*}\))t, wherek _B \(T_{*}\) = Gm ₁ m ₂/2 is a critical temperature, and an anomalousdiffusion for large times \(\langle\) r ² \(\rangle\) \(\propto\) \(t^{1-T_*/T}\). As a by-product, our solution also describes thegrowth of the Dirac peak (condensate) that forms at large time inthe post collapse regime of the Smoluchowski-Poisson system (orKeller-Segel model in biology) for T < T _c = GMm/(4k _B ). We find thatthe saturation of the mass of the condensate to the total mass isalgebraic in an infinite domain and exponential in a boundeddomain. Finally, we provide the general form of the virial theoremfor Brownian particles with power law interactions.     

Influence of the dimension of a polycrystalline film and the optical anisotropy of crystallites on the effective dielectric constant of the film

The dimension D of a polycrystalline film and the optical anisotropy m = ε_z/ε_x of uniaxial crystallites with the principal components ε_x = ε_y and ε_z of the tensor of the dielectric constant have been shown to produce a strong influence on the effective dielectric constant ε_D^* and the effective refractive index n_D^* = (ε_D^*)^1/2 of the film in the optical transparency region, as well as on the boundaries of the intervals B_Dl ≤ ε_D^* ≤ B_Du. The intervals Δ₂(m) = B_2l–B_2u and Δ₃(m) = B_3l–B_3u are separated by a gap for m in the range 1 < m < 2, whereas the theoretical dependence ε₂^*(m) is separated by a gap from the interval Δ₃(m) for m in the range 1 < m < 4. This is confirmed by a comparison of the experimental (n_oP) and theoretical (n_D^*) ordinary refractive indices for uniaxial polycrystalline films of the conjugated polymer poly(p-phenylene vinylene) (PPV) with uniaxial crystallites and appropriate values of m. In the visible transparency region of the PPV films with a change in m(λ) in the range 2 < m(λ) < 3 due to the dependence of the components ε_x,z(λ) on the light wavelength λ, the refractive indices n_oP²(λ) = ε_oP(λ) are consistent with the theoretical values of ε₂^*(λ) and lie outside the interval Δ₃(m). For m(λ) > 3 near the electronic absorption band of the crystallites, the values of ε_oP(λ) lie in the region of the overlap of the intervals Δ₂(m) and Δ₃(m). The boundaries mc of the range 1 < m < m_c are determined, for which the interval Δ₂(m) is separated by a gap from the dependences ε₃^*(m) corresponding to the effective medium theory with spherical crystallites and hierarchical models of a polycrystal, as well as from the proposed new dependence ε₃^*(m).     

Magnetoresistance of a highly correlated electron liquid

The behavior in a magnetic field of a highly correlated electron liquid approaching the fermion condensation quantum phase transition from the disordered phase is considered. We show that, at sufficiently high temperatures T≥T*(x), the effective mass starts to depend on T, M* ∝T^?1/2. This T^?1/2 dependence of the effective mass at elevated temperatures leads to the non-Fermi liquid behavior of the resistivity, σ(T) ∝ T and at higher temperatures σ(T) ∝ T^3/2. The application of a magnetic field B restores the common T² behavior of the resistivity. The effective mass depends on the magnetic field, M*(B) ∝ B^?2/3, being approximately independent of the temperature at T≤T*(B) ∝ B^4/3. At T≥T*(B), the T^?1/2 dependence of the effective mass is reestablished. We demonstrate that this B-T phase diagram has a strong impact on the magnetoresistance (MR) of the highly correlated electron liquid. The MR as a function of the temperature exhibits a transition from negative values of MR at T→0 to positive values at T ∝ B^4/3. Thus, at T≥T*(B), MR as a function of the temperature possesses a node at T ∝ B^4/3.     

Microhardness and refractive index of titanium dioxide-based binary coatings

Glass composites covered by sol–gel TiO₂–m Me _x O _y (Me _x O _y = ZnO, CdO, SnO, CuO, and Fe₂O₃ and m = 2, or 10 wt %) binary oxide coatings have been studied. The microhardness of the composites and glass substrate has been measured, and the microhardness of the coatings has been determined from these measurements. A correlation between the microhardness of the coatings, their refractive index, and packing density of disperse sol phase particles in the coating has been established.     

Magnetic characteristics of MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles obtained by glycine–nitrate synthesis

The magnetic properties of magnesium–iron spinel (MgFe₂O₄) powdered nanoparticles obtained by glycine–nitrate synthesis are investigated by X-ray phase analysis and the NMR method. According to the results of X-ray phase analysis, the average size of the crystalline part of nanoparticles of the powder under investigation is 45 ± 4 nm. Magnetization J is determined using the formula J = (B/μ0)–H, where B and H are the induction and strength of the magnetic field in the sample, which are measured by the NMR method. The magnetic characteristics of MgFe₂O₄ are as follows: specific saturation magnetization J_sat = 17.52 A m²/kg, specific residual magnetization J_r = 5.73 A m2/kg, coercive force H_c = 4600 A/m, and magnetic moment P_sat = 371 × 10^–20 A m² in the magnetic saturation state and P_r = 121 × 10^–20 A m² in the residual magnetization state.     

Anomalous thermopower in heavy-fermion compounds CeB<Subscript>6</Subscript>, CeAl<Subscript>3</Subscript>, and CeCu<Subscript>6 − <Emphasis Type="Italic">x</Emphasis></Subscript>Au<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

High-precision measurements of thermopower have been performed in a wide temperature range (2–300 K) for a series of cerium-based heavy-fermion compounds, including CeB₆, CeAl₃, CeCu₆, and substitutional solid solutions of the CeCu_{6 ? x} Au _x system (x = 0.1, 0.2). All compounds exhibit an unusual (logarithmic) asymptotic behavior of the temperature dependence of the Seebeck coefficient: S ∝ ?lnT. In the case of cerium hexaboride, this anomalous behavior of S(T) is accompanied by the appearance of weak-carrier-localization-mode asymptotics in the conductivity (σ(T) ∝ T ^0.39), while the paramagnetic susceptibility χ(T) and the effective mass of charge carriers m _eff(T) vary according to a power law (χ(T), m _eff(T) ∝ T ^?0.8) in the temperature interval T = 10–80 K. This behavior corresponds to renormalization of the density of states at the Fermi level. The observed anomalous behavior of thermopower in CeB₆ and other cerium-based intermetallic compounds is attributed to the formation of heavy fermions (many-body states in the metal matrix) at low temperatures.     

Dielectric relaxations,magnetodielectric and magnetoelectric interactions in Bi0.6La0.4MnO3 ceramics

Complex permittivity ε*/ε₀ = ε′/ε₀–iε″/ε₀ of the bismuth–lanthanum manganite Bi_0.6La_0.4MnO₃ ceramics has been measured in the temperature range of 10–220 K at frequencies f = 20–10⁶ Hz and magnetic inductions B = 0–0.846 T. At a temperature of 80 K, the spectra ε′/ε₀(t) and ε″/ε₀(t) demonstrate the dielectric relaxation that is a superposition of contributions of several relaxation processes, each of which is dominant in its frequency range: I (f < 10³ Hz, II (10³ < f < 10⁵ Hz), and III (10⁵ < f < 10⁶ Hz). In the range of 10–120 K, anomalous behavior of ε′/ε₀(T) and ε″/ε₀(T) is observed near the temperature of the transition from the paramagnetic to ferromagnetic phase and is due to the Anderson localization of charge carrier on a spin disorder.     

Diffraction enhancement effect and new possibilities of measuring the electric charge of the neutron and its inertial-to-gravitational mass ratio

Diffraction enhancement of small effects affecting a neutron undergoing Laue diffraction at Bragg angles θ _B close to 90° is predicted and experimentally observed. The enhancement is due to the delay of the neutron inside the crystal during diffraction and is proportional to tan² θ _B. As a result, the diffraction enhancement factor may be as large as ～10⁸–10⁹. On this basis, a new method is proposed for searching for the electric charge of the neutron and for measuring the ratio of its inertial mass m _i to the gravitational mass m _G . It is shown that the accuracy of the neutron charge measurement can be improved by more than two orders of magnitude in relation to the present-day accuracy and that the ratio m _i /m _G can be measured to an precision of σ(m _i /m _G ) ～ 10^?6.     

Low-Temperature Transport Properties of Lanthanum Hexaboride La<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ce<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>B<Subscript>6</Subscript> Single Crystals

Resistivity (ρ), thermal conductivity (k) and Seebeck coefficient (S) of La_1–xCe_xB₆ single crystals with various concentrations of cerium Ce ions was measured in a wide temperature range 3?300 K. The obtained data were analyzed in the framework of the Coqblin–Shrieffer model. The contributions of scattering of carriers on magnetic ions Ce for all transport parameters ρ(T), k(T), S(T) are revealed. Strong dependence of the magnetic scattering on concentration of the cerium ions are identified. The anomalous behavior of the transport parameters ρ(T), k(T), S(T) in the region near 30 K is attributed to the Δ ~ 30 K splitting of Г₈ level.     

Effect of vibronically induced spin-orbit coupling of electronic ππ* states on nonradiative intersystem crossing: Naphthalene

The effect of (I) S ₁(¹ B _2u ) ? T ₁(³ B _1u ) and (II) S ₁ ? T ₂ (³ B _3g ) ? T ₁ transitions in naphthalene on the rate constant K _ST ^s of the S ₁ ? T ₁ nonradiative transitions to all triplet sublevels s = z, y, x of the T ₁ state has been investigated in the approximation of vibronically induced spin-orbit couplings, taking into account all out-of-plane vibrational modes. The shapes of the vibrational modes that are most active in these transitions are determined. The calculated values K _ST = (0.33–0.75) × 10⁷ s^?1, obtained with allowance for the I and I + II transitions, are consistent with the experimental values (K _ST)_exp found by different researchers. It is established in all calculation versions that K _ST > K _ST ^z > k _ST ^x . This relation is in qualitative agreement with the known magnetooptical data.     

Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

Anomalously slow relaxation of a nonwetting liquid in the disordered confinement of a nanoporous medium

The time evolution of the water–disordered nanoporous medium Libersorb 23 (L23) system has been studied after complete filling at elevated pressure followed by full release of overpressure. It is established that relaxation of the L23 rapidly flows out during the overpressure relief time, following the variation in pressure. At a temperature below that of the dispersion transition (T < T _d = 284 K), e.g., at T = 277 K, the degree of filling θ decreases from 1 to 0.8 within 10 s. The degree of filling varies with time according to the power law θ ~ t ^–α with the exponent α < 0.1 over a period of t ~ 10⁵ s. This process corresponds to slow relaxation of a metastable state of a nonwetting liquid in a porous medium. At times t > 10⁵ s, the metastable state exhibits decay, manifested as the transition to a power dependence of θ(t) with a larger exponent. The relaxation of the metastable state of nonwetting liquid in a disordered porous medium is described in the mean field approximation as a continuous sequence of metastable states with a barrier decreasing upon a decrease in the degree of filling. Using this approach, it is possible to qualitatively explain the observed relaxation process and crossover transition to the stage described by θ(t) with a larger exponent.     

A nonradiative intersystem crossing <Emphasis Type="Italic">S</Emphasis>(ππ*) ↝ <Emphasis Type="Italic">T</Emphasis>(ππ*) transition in dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxin

The probability of the nonradiative S-T intersystem crossing in dibenzo-p-dioxin is theoretically studied using a model for the vibronically induced spin-orbit coupling between electronic states and taking into account all out-of-plane vibrational modes. Several symmetry variants for the lowest S ₁(ππ*) singlet state are considered. In the case of g symmetry of this state, a provision is made for the possibility of its vibronic coupling with the nearest dipole-active singlet ¹ B _2u ππ* state. The rate constants K _ST of the S ₁ ? T(ππ*) transitions to the T ₁(³ B _3g ) state are estimated taking into account several intermediate triplet T _m (ππ*) states of g and u symmetry. For different symmetry types of the S ₁ state, the effect of K _ST on the fluorescence quantum yield ?_fl is discussed. The ¹ B _3g symmetry state is found to be the lowest S ₁ state. It is found that the main contribution to K _ST is made by the S ₁(¹ B _3g ) ? T ₄(³ A _g ) transition.     

The 2<Superscript>1/3</Superscript> rule and other properties of ferromagnets near the temperature of the maximum of magnetic susceptibility

The behavior of the magnetization M and the magnetic susceptibility χ is theoretically analyzed for ferromagnets at the temperature T=T _m corresponding to the maximum of the function χ(T). Four new methods of determining the Curie temperature T_C with the use of the derived relationships are proposed. One of these methods is based on the relationship χ(T _m ) =2^1/3χ(T_C) (the 2^1/3 rule). The results are applied for processing experimental data obtained for lanthanum manganite of composition La_0.85Sr_0.15MnO₃.