Temperature Dependence Of Relaxation Rate Research Articles

Illuminating Ligand Field Contributions to Molecular Qubit Spin Relaxation via T1 Anisotropy.

Electron spin relaxation in paramagnetic transition metal complexes constitutes a key limitation on the growth of molecular quantum information science. However, there exist very few experimental observables for probing spin relaxation mechanisms, leading to a proliferation of inconsistent theoretical models. Here we demonstrate that spin relaxation anisotropy in pulsed electron paramagnetic resonance is a powerful spectroscopic probe for molecular spin dynamics across a library of highly coherent Cu(II) and V(IV) complexes. Neither the static spin Hamiltonian anisotropy nor contemporary computational models of spin relaxation are able to account for the experimental T1 anisotropy. Through analysis of the spin-orbit coupled wave functions, we derive an analytical theory for the T1 anisotropy that accurately reproduces the average experimental anisotropy of 2.5. Furthermore, compound-by-compound deviations from the average anisotropy provide a promising approach for observing specific ligand field and vibronic excited state coupling effects on spin relaxation. Finally, we present a simple density functional theory workflow for computationally predicting T1 anisotropy. Analysis of spin relaxation anisotropy leads to deeper fundamental understanding of spin-phonon coupling and relaxation mechanisms, promising to complement temperature-dependent relaxation rates as a key metric for understanding molecular spin qubits.

Air-Stable Dy(III)-Macrocycle Enantiomers: From Chiral to Polar Space Group

Air-Stable Dy(III)-Macrocycle Enantiomers: From Chiral to Polar Space Group

Absence of μSR evidence for magnetic order in the pseudogap phase of Bi2+xSr2−xCaCu2O8+δ

We present an extended zero-field muon spin relaxation (ZF-$\mu$SR) study of overdoped Bi$_{2+x}$Sr$_{2-x}$CaCu$_2$O$_{8+\delta}$ (Bi2212) single crystals, intended to elucidate the origin of weak quasistatic magnetism previously detected by $\mu$SR in the superconducting and normal states of optimally-doped and overdoped samples. New results on heavily-overdoped single crystals show a similar monotonically decreasing ZF-$\mu$SR relaxation rate with increasing temperature that persists above the pseudogap (PG) temperature $T^*$ and does not evolve with hole doping ($p$). Additional measurements using an ultra-low background apparatus confirm that this behavior is an intrinsic property of Bi2212, which cannot be due to magnetic order associated with the PG phase. Instead we show that the temperature-dependent relaxation rate is most likely caused by structural changes that modify the contribution of the nuclear dipole fields to the ZF-$\mu$SR signal. Our results for Bi2212 emphasize the importance of not assuming the nuclear-dipole field contribution is independent of temperature in ZF-$\mu$SR studies of high-temperature (high-$T_c$) cuprate superconductors, and do not support a recent $\mu$SR study of YBa$_2$Cu$_3$O$_{6+x}$ that claims to detect magnetic order in the PG phase.

On the Planckian Limit for Inelastic Relaxation in Metals

We consider the simplest model for $T$ - linear growth of resistivity in metals. It is shown that the so called "Planckian" limit for the temperature dependent relaxation rate of electrons follows from a certain procedure for representation of experimental data on resistivity and, in this sense, is a kind of delusion.

INVESTIGATION OF TEMPERATURE DEPENDENCE OF D2O SOLUTIONS BY 400 MHZ NMR

The rate of water proton relaxation of protein solutions were studied in the presence and absence of the paramagnetic ions[ gadolinium (III), manganese (II), chromium (III), iron (III), nickel (II), copper (II), and cobalt (II)] in the previous studies. However, these studies were carried out rather at low frequencies. Therefore, studying of temperature dependence of relaxation rates for absence and presence of 2 % albumin in pure D 2 O by 400 MHz will be a novelty. In this study, T 1 and T 2 relaxation ratios of D 2 O and 0.1 H 2 O / 0.9D 2 O solutions were investigated with respect to temperature for pure and for constant albumin concentration(2%). The experiments were carried out by using Bruker Avance 400 MHz NMR. Inversion Recovery (180-τ-90) pulse step were used for T 1 , whereas Carr-Purcell-Meiboom-Gill pulse step were used for T 2 . The experiments were performed for temperature range of 20°C-40°C by using automatic temperature control unit. 1/T 1 and 1/T 2 decrease linearly with increasing temperature for pure D 2 O solutions. However, for 0.1H 2 O/0.9D 2 O solutions, the relaxation rates of T 1 increase with increasing temperature while T 2 decreases with increasing temperature. The decrease in both relaxation rates of the D 2 O solution with respect to the increased temperature suggests that relaxation is due to spin relaxation interaction. Increasing of relaxation rates with the increasing temperature, in the presence of albumin demonstrates the validity of the dipolar mechanism

Experimental study of relaxation dynamics in solid solutions of benzene, hexa-substituted benzenes. II

In continuation with Part I of current study, we present here the orientationally disordered materials pentachloroaniline (PCA), bromopentamethylbenzene (BPMB), and their solid solutions with hexachlorobenzene (HCB) and hexamethylbenzene (HMB), respectively, encompassing the entire concentration range, studied employing dielectric spectroscopy, differential scanning calorimetry, and powder X-ray spectroscopy. The α- relaxation in these systems gets closer to Debye behaviour on non-polar rich side and is analyzed employing Havriliak-Negami equation, whereas the β- relaxation is found to be symmetric everywhere and follows Cole–Cole equation. In both the systems studied here, the temperature dependence of relaxation rates could be described by Arrhenius equation. The β- relaxation evidenced in these two binary systems appears to originate from the different microscopic mechanism that is discussed based on their spectral behaviour. Further, we probe the liquid glasses of very dilute concentrations of dipolar HSB solutes in OTP matrix, and compare it with the spectral features of the dilute dipolar solid solutions of HSBs.

Ultrafast dynamics in the presence of antiferromagnetic correlations in electron-doped cuprate La2−xCexCuO4±δ

We used femtosecond optical pump-probe spectroscopy to study the photoinduced change in reflectivity of thin films of the electron-doped cuprate La$_{2-x}$Ce$_x$CuO$_4$ (LCCO) with dopings of x$=$0.08 (underdoped) and x$=$0.11 (optimally doped). Above T$_c$, we observe fluence-dependent relaxation rates which onset at a similar temperature that transport measurements first see signatures of antiferromagnetic correlations. Upon suppressing superconductivity with a magnetic field, it is found that the fluence and temperature dependence of relaxation rates is consistent with bimolecular recombination of electrons and holes across a gap (2$\Delta_{AF}$) originating from antiferromagnetic correlations which comprise the pseudogap in electron-doped cuprates. This can be used to learn about coupling between electrons and high-energy ($\omega>2\Delta_{AF}$) excitations in these compounds and set limits on the timescales on which antiferromagnetic correlations are static.

(1)H NMR Relaxometric Study of Molecular Dynamics in a "de Vries" Liquid Crystal.

Liquid crystals that exhibit de Vries smectic A phases are promising materials for new generations of ferroelectric liquid crystal displays and other electro-optical devices. We investigated the molecular dynamic properties of a rod-like de Vries liquid crystal compound, namely the 9HL, a (S)-hexyl lactate derivative, in the whole mesophasic range. This is the first molecular dynamics' investigation on a de Vries phase, and the interest of this system is related to the understanding of the structural and supramolecular organization of de Vries SmA phases, which has been a subject of a broad scientific debate in the last years. Proton NMR spin-lattice relaxation times, T1, were measured in the range 100 MHz to 5 kHz, thus covering a very wide range of motional regimes. (1)H NMR dispersion curves and temperature-dependent relaxation rates were analyzed with a global minimum target fitting approach and the main molecular motions, namely reorientational diffusion, translational self-diffusion, layer undulation, and tilting director fluctuations were fully characterized. The molecular dynamics' behavior observed across the SmA-SmC* phase transitions of 9HL was consistent with the proposed cluster diffuse cone model for the de Vries SmA phase.

Electronic and Ionic Conductivity in Alkaline Earth Diazenides MAEN2(MAE= Ca, Sr, Ba) and in Li2N2

Electrical conductivity measurements of alkaline earth diazenides SrN2 and BaN2 revealed temperature-dependent metal-like behavior. As CaN2 is isotypic with SrN2 its electronic properties are supposed to show similar characteristics. For the alkali diazenide Li2N2, the corresponding measurement shows not only the typical characteristics of metallic materials but also an unexpected rise in electrical conductivity above 250 K, which is consistent with an ionic contribution. This interpretation is further corroborated by static 6Li and 7Li nuclear magnetic resonance measurements (NMR) of the spin-lattice relaxation time (T1) over an extended temperature range from 50 to 425 K. We observe a constant Heitler-Teller product (T1T) as expected for metals at low temperatures and a maximum in the temperature-dependent relaxation rates, which reflects the suggested ionic conductivity. A topological structural analysis indicates possible 3D ion migration pathways between two of the three crystallographic independent Li positions. A crude estimate of temperature-dependent self-diffusion coefficients D(T) of the lithium motion classifies Li2N2 as a mixed electronic/ionic conductor.

The Temperature Dependence of Optical Phonon Scattering in Graphene under Strong Magnetic Field

We theoretically investigate the electron relaxation mechanism assisted by optical phonon scattering among Landau levels in graphene. The relaxation rate displays a Gaussian distribution by considering the effect of lattice relaxation that arises from the electron-deformation potential acoustic phonon coupling. We find that the present model can gives both increasing and decreasing temperature dependence of the relaxation process mediated by phonon emission. Moreover, the deformation potential constant of the acoustic phonon plays an important role in determining the temperature dependence of relaxation rate.

Dielectric relaxation and conductivity in the PbCo0.5Ta0.5O3 ceramics

Abstract For the first time results of the dielectric properties of PbCo 0.5 Ta 0.5 O 3 ceramics are reported in the frequency range of 200 Hz–1 MHz at temperatures 300–450 K. The frequency-dependent electrical data is discussed in the framework of the non-Debye relaxation using complex dielectric permittivity and electric modulus representations. The dielectric permittivity shows strong dispersion above room temperature with Arrhenius temperature dependent relaxation rate. The dielectric spectra at the low frequencies and at the high temperatures are highly influenced by the ionic conductivity. Frequency-dependent conductivity and non-Arrhenius mean electric relaxation time, obtained by the complex modulus M ⁎ ( ω ), are analyzed and similarities to ion glass state are pointed out.

ESR study of spin relaxation in graphene

We report pulse ESR studies of the electron spin relaxation processes in graphene. The linear temperature dependences of relaxation rates corresponding to T1≈T2∼0.1–1μs, similar values of g-factors of possible paramagnetic centres, and the Lorentzian lineshape of the signal indicate the bottleneck effect in spin relaxation of the strongly coupled homogeneous spin system of localized spins and conduction electrons. Interpretation of the data in the frames of the theory of strongly interacting localized and delocalized magnetic moments gives the spin relaxation time of the conduction electrons of an order of 5–30ns, depending on the paramagnetic centres concentration.

Measurements of Raman scattering by electrons in metals: The effects of electron-phonon coupling

We report the first systematic measurements of the Raman scattering by electrons in elemental metals of Al, Mo, Nb, Os, Pb, Re, Ta, Ti, V, W and metallic compound La$B_6$. Experimental spectra are modelled on the base of the band structures, calculated within the density functional theory, taking properly into account the effects of electron-phonon scattering. The agreement between our measured and calculated spectra is excellent for the variety of metals, thus providing estimates for the electron-phonon coupling constants and temperature-dependent relaxation rates. The method can be applied for other metallic materials to evaluate an electron-phonon coupling as an alternative to the transport and optical measurements.

Flux dynamics and vortex phase diagram inBa(Fe1−xCox)2As2single crystals revealed by magnetization and its relaxation

Magnetization and its relaxation have been measured in $Ba(Fe_{1-x}Co_x)_2As_2$ single crystals at various doping levels ranging fromvery underdoped to very overdoped regimes. Sizable magnetization relaxation rate has been observed in all samples, indicating a moderate vortex motion and relatively small characteristic pinning energy. Detailed analysis leads to the following conclusions: (1) A prominent second-peak (SP) effect was observed in the samples around the optimal doping level (x $\approx$ 0.08), but it becomes invisible or very weak in the very underdoped and overdoped samples; (2) The magnetization relaxation rate is inversely related to the transient superconducting current density revealing the non-monotonic field and temperature dependence through the SP region; (3) A very sharp magnetization peak was observed near zero field which corresponds to a much reduced relaxation rate; (4) A weak temperature dependence of relaxation rate or a plateau was found in the intermediate temperature region. Together with the treatment of the Generalized-Inversion-Scheme, we suggest that the vortex dynamics is describable by the collective pinning model. Finally, vortex phase diagrams were drawn for all the samples showing a systematic evolution of vortex dynamics.

Local magnetism and magnetoelectric effect inHoMnO3studied with muon-spin relaxation

We present the results of muon-spin relaxation (muSR) measurements on the hexagonal manganite HoMnO3. Features in the temperature-dependent relaxation rate, lambda, correlate with the magnetic transitions at 76 K, 38 K and 34 K. The highest temperature transition, associated with the ordering of Mn3+ moments has the largest effect on lambda. The application of a static electric field of E=10^4 Vm^-1 below T=50 K causes a small reduction in lambda which is suggestive of coupling between ferroelectric and magnetic domain walls in the ordered state of the material.

Impact of Chlorine Substitution on Spin–Lattice Relaxation of Triarylmethyl and 1,4-Benzosemiquinone Radicals in Glass-Forming Solvents Between 25 and 295 K

Spin-lattice relaxation rates measured by long-pulse saturation recovery in glassy solvents for chlorinated aromatic radicals: perchlorotriphenylmethyl radical, 2,5-dichloro-3,6-dihydroxy-1,4-benzosemiquinone, and tetrachloro-1,4-benzosemiquinone, were compared with relaxation rates for non-chlorinated analogs. The impact of the quadrupolar chlorines is small, and less than the effects of changing the rigidity of the glass. The temperature dependence of relaxation rates below the glass transition temperature could be modeled as the sum of contributions from the direct, Raman, and local mode processes.

Observation of temperature-independent internal Er3+ relaxation efficiency in Si-rich SiO2 films

Time-dependent photoluminescence measurements of low-temperature-annealed Er-doped Si-rich SiO2 were conducted at sample temperatures 15–300 K. The erbium internal relaxation efficiency from the second (I411/2) to the first (I413/2) excited state upon luminescence-center-mediated Er3+ excitation is investigated. Despite the observation of temperature-dependent relaxation rates, the erbium internal relaxation efficiency is found to be remarkably temperature independent, which suggests that the internal relaxation efficiency is near unity. Internal relaxation is shown to account for 50%–55% of the I413/2 excitation events in the entire temperature range. These results demonstrate that high pump efficiency and stable operation of devices based on this material will be possible under varying thermal conditions.

Measuring Ti(III)−Carotenoid Radical Interspin Distances in TiMCM-41 by Pulsed EPR Relaxation Enhancement Method

Interspin distances between the Ti(3+) ions and the carotenoid radicals produced inside TiMCM-41 pores by photoinduced electron transfer from 7'-apo-7'-(4-carboxyphenyl)-beta-carotene (coordinated to Ti(3+)), canthaxanthin (formed as a random distribution of isomers), and beta-ionone (model for a short-chain polyene) to Ti(3+) framework sites were determined using the pulsed EPR relaxation enhancement method. To estimate the electron transfer distances, the temperature dependence of relaxation rates was analyzed in both siliceous and metal-substituted siliceous materials. The phase memory times, T(M), of the carotenoid radicals were determined from the best fits of two-pulse ESEEM curves. The spin-lattice relaxation times, T(1), of the Ti(3+) ion were obtained from the inversion recovery experiment with echo detection on a logarithmic time scale in the temperature range of 10-150 K. The relaxation enhancement for the carotenoid radicals in TiMCM-41 as compared to that in MCM-41 is consistent with an interaction between the radical and the fast relaxing Ti(3+) ion. For canthaxanthin and beta-ionone, a dramatic effect on the carotenoid relaxation rate, 1/T(M), occurs at 125 and 40 K, respectively, whereas for carboxy-beta-carotene 1/T(M) increases monotonically with increasing temperature. The interspin distances for canthaxanthin and beta-ionone were estimated from the 1/T(M) - 1/T(M0) difference, which corresponds to the Ti(3+) contribution at the temperature where the maximum enhancement in the relaxation rate occurs. Determination of the interspin distances is based on calculations of the dipolar interaction, taking into consideration the unpaired spin density distribution along the 20-carbon polyene chain, which makes it possible to obtain a fit over a wider temperature interval. A distribution of the interspin distances between the carotenoid radical and the Ti(3+) ion was obtained with the best fit at approximately 10 A for canthaxanthin and beta-ionone and approximately 9 A for 7'-apo-7'-(4-carboxyphenyl)-beta-carotene with an estimated error of +/-3 A. The interspin distances do not depend on 1/T(M) - 1/T(M0) for carboxy-beta-carotene which shows no prominent peak in the relaxation rate over the temperature range measured.

Parameters of the temperature dependence of the rate of magnetic relaxation of protons in water and its solutions including seawater

The results of measurements of the temperature dependence of the relaxation rate (1/T1) of protons in seawater with 35‰ salinity and salt solutions with different concentrations at temperatures from −22°C to +120°C are presented. The possibility of approximating the temperature dependence of the magnetic relaxation rate by different functions in pure water, seawater, and solutions of the salts of the latter was studied. The parameters of this dependence and their variation under the influence of salt components are given. The least mean square deviation was obtained, and the best convergence was determined according to the statistical criteria for aqueous electrolytes of moderate concentrations for the function in the form of the sum of exponentials, in which the number of terms depended on the solution concentration. It is shown that the parameters of the thermal dependence of the relaxation rate represented by different functions can be used in combination for studying the dynamic properties of the solutions of low and moderate concentrations.

Theory of damped Rabi oscillations at finite temperatures

Rabi oscillations in the presence of dissipation are theoretically studied at finite temperatures. The system that we consider is a quantum two-level system with both internal relaxations and external decays under an alternating field. The environment modeled by a set consisting of an infinite number of harmonic oscillators is employed in order to introduce temperature into the system. The equations of motion for the density matrix (Liouville equation) of such a quantum two-level system coupled to a Caldeira-Leggett-type environment are obtained with the Born-Markov approximation. Internal relaxations of the system are incorporated into the Liouville equations using the Redfield theory, resulting in Liouville equations with temperature-dependent relaxation rates. The exact solutions are obtained by using the Torrey method based on the Laplace transform. The solution for damped Rabi oscillations can be divided into elementary relaxation processes such as a simple decay and a damped oscillation. Since the coefficients of the solution involve physical relaxation rates corresponding to the processes, all the relaxation rates such as the dephasing rate are determined by simple calculations of the coefficients in these different relaxation processes.