Spin-lattice relaxation by tunnelling motions of methyl groups in some organic compounds

The proton spin-lattice relaxation times, T₁, of methyl groups in (CH₃CO)₂O, CH₃COCl, CH₃ COBr and (CH₃)₂S₂ have been measured below melting points at 52 MHz. The observed T₁ minima display the presence of tunnelling rotation. From the fit of the experimental results the ground, the first excited state tunnelling frequencies and the energy difference between the ground and the first excited states of the compounds have been estimated.     

Analysis of microsecond relaxation dynamics of proteins and viscous media by recording relaxation shifts of phosphorescence spectra

We studied the low-temperature dynamics of the Stokes shift of instantaneous phosphorescence spectra of eosin and eosin maleimide covalently bound to hemoglobin in a 66% v/v aqueous solution of glycerol under conditions of pulsed excitation. The kinetics of the Stokes shifts are described using the Cole-Davidson distribution function. From the experimental data, we obtain the parameters τ₀ and β, which describe the Cole-Davidson distribution. Values of τ₀ and β agree well with data obtained by other methods, and these parameters can be used to describe electron transfer reactions in polar solutions and proteins.     

Electron spin-lattice relaxation in radicals containing two methyl groups,generated by gamma-irradiation of polycrystalline solids

The effects of methyl rotation on electron spin-lattice relaxation times were examined by pulsed electron paramagnetic resonance for the major radicals in gamma-irradiated polycrystalline alpha-amino isobutyric acid, dimethyl-malonic acid, and L-valine. The dominant radical is the same in irradiated dimethyl-malonic acid and alpha-amino isobutyric acid. Continuous wave saturation recovery was measured between 10 and 295 K at S-band and X-band. Inversion recovery, echo-detected saturation recovery, and pulsed electron-electron double resonance (ELDOR) data were obtained between 77 and 295 K. For the radicals in the three solids, recovery time constants measured by the various techniques were not the same, because spectral diffusion processes contribute differently for each measurement. Hyperfine splitting due to the protons of two methyl groups is resolved in the EPR spectra for each of the samples. Pulsed ELDOR data were obtained to characterize the spectral diffusion processes that transfer magnetization between hyperfine lines. Time constants were obtained for electron spin-lattice relaxation (T(1e)), nuclear spin relaxation (T(1n)), cross-relaxation (T(x1)), and spin diffusion (T(s)). Between 77 and 295 K rapid cross-relaxation (deltaM(s) = +/- 1, deltaM(I) = -/+ 1) was observed for each sample, which is attributed to methyl rotation at a rate that is approximately equal to the electron Larmor frequency. The large temperature range over which cross-relaxation was observed suggests that methyl groups in the radical and in the lattice, with different activation energies for rotation, contribute to the rapid cross-relaxation. Activation energies for methyl and amino group rotation between 160 and 1900 K (1.3-16 kJ/mol) were obtained by analysis of the temperature dependence of 1/T(1e) at S-band and X-band in the temperature intervals where the dynamic process dominates T(1e).     

Internal dynamics and hydration of solid proteins by1H NMR relaxation and FTIR spectroscopy

Temperature dependences of¹H nonselective nuclear magnetic resonanceT ₁ andT ₂ relaxation times measured at 27 MHz have been studied on solid human serum albumin (HSA) samples at various hydrations. The data were interpreted in terms of three kinds of internal motions in a protein and microdynamic parameters of the motions were obtained by a “model-free” approach. Two fast motions with correlation times lying in the range of tens to hundreds picoseconds were shown to be essentially insensitive to hydration. Unlike lysozyme and bovine albumin, HSA reveals relaxation transition due to slow motion in the room temperature range thus allowing one to obtain microdynamic parameters more precisely. Hydration leads to a shortening of the correlation time from hundreds to tens nanoseconds and to a less restricted movement. The comparison of the hydration dependence of relaxation parameters with infrared spectra of HSA side chain groups clearly shows that methyl protons are evidently involved in a slow motion, following the saturation of the protein globule surface by water. The same dependence correlating with solvent accessible surface areas was shown to exist for some other proteins. In addition to the main set of protons performing a solidlike movement, a small amount of much more mobile protons is also present with its proportion rising steeply with hydration and temperature. The origin of these protons is discussed.     

Spin-lattice relaxation study of the methyl proton dynamics in solid 9,10-dimethyltriptycene (DMT)

Proton spin-lattice relaxation studies are performed for powder samples of 9,10-dimethyltriptycene (DMT) and its isotopomer DMT-d₁₂ in which all the non-methyl protons in the molecule are replaced by deuterons. The relaxation data are interpreted in terms of the conventional relaxation theory based on the random jump model in which the Pauli correlations between the relevant spin and torsional states are discarded. The Arrhenius activation energies, obtained from the relaxation data, 25.3 and 24.8 kJ mol^?1 for DMT and DMT-d₁₂, respectively, are very high as for the methyl groups. The validity of the jump model in the present case is considered from the perspective of Haupt theory in which the Pauli principle is explicitly invoked. To this purpose, the dynamic quantities entering the Haupt model are reinterpreted in the spirit of the damped quantum rotation (DQR) approach introduced recently for the purpose of NMR lineshape studies of hindered molecular rotators. Theoretical modelling of the relevant methyl group dynamics, based on the DQR theory, was performed. From these calculations it is inferred that direct assessments of the torsional barrier heights, based on the Arrhenius activation energies extracted from relaxation data, should be treated with caution.     

Evaluation of cross-correlation effects and measurement of one-bond couplings in proteins with short transverse relaxation times

Various strategies are described and compared for measurement of one-bond J(NH) and J(NC') splittings in larger proteins. In order to evaluate the inherent resolution obtainable in the various experiments, relaxation rates of (15)N-(1)H(N) coupled and heteronuclear decoupled resonances were measured at 600- and 800-MHz field strengths for both perdeuterated and protonated proteins. A comparison of decay rates for the two (15)N-?H(N)? doublet components shows average ratios of 4.8 and 3.5 at 800- and 600-MHz (1)H frequency, respectively, in the perdeuterated proteins. For the protonated proteins these ratios are 3.2 (800 MHz) and 2.4 (600 MHz). Relative to the regular HSQC experiment, the enhancement in TROSY (15)N resolution is 2.6 (perdeuterated; 800 MHz), 2.0 (perdeuterated; 600 MHz), 2.1 (protonated; 800 MHz), and 1.7 (protonated; 600 MHz). For the (1)H dimension, the upfield (1)H(N)-?(15)N? component on average relaxes slower than the downfield (1)H(N)-?(15)N? component by a factor of 1.8 (perdeuterated; 800 MHz) and 1.6 (perdeuterated; 600 MHz). The poor resolution for the upfield (15)N-?(1)H? doublet component in slowly tumbling proteins makes it advantageous to derive the J(NH) splitting from the difference in frequency between the narrow downfield (15)N doublet component and either the (1)H-decoupled (15)N resonance or the peak position in an experiment which J-scales the frequency of the upfield doublet component but maintains some of the advantages of the TROSY experiment.     

Ion dynamics in solid electrolytes described by the concept of mismatch and relaxation

Abstract

Below the far-infrared frequency regime, conductivity spectra of crystalline ion conductors like RbAg₄I₅ and others display remarkably uniform characteristics. Well-known approximations include the universal dynamic response (UDR) and the nearly constant loss (NCL) behaviour. We now present a new non-power-law, non-KWW master curve. Its shape is shown to be equivalent to a proportionality between two particular functions of time. These functions are interpreted as rates of mismatch relaxation via the so-called single-particle and many-particle routes. The proportionality of relaxation rates is the central statement of the concept of mismatch and relaxation (CMR).     

Photoexcited carrier relaxation dynamics in pentacene probed by ultrafast optical spectroscopy: Influence of morphology on relaxation processes

We present a comparative study of ultrafast photoexcited state relaxation in pentacene single crystals and in pure and C₆₀-doped pentacene films using optical pump-probe spectroscopy. The photoinduced absorption spectra in pentacene crystals is consistent with a dominant singlet-triplet fission decay channel for above-gap excitation. This decay channel is suppressed in thin films and even further suppressed by electron trapping in C₆₀-doped films. Thus we show that suppression of triplet state production, which is necessary for free carrier formation and thus photovoltaic and photodiode performance, is controllable via sample morphology.     

Rotational tunneling dynamics of methyl groups inn-alkane host lattices: An optical investigation of the internal and external isotope effect

We exploited the slow relaxation of methyl group rotational tunneling states to perform optical hole burning inn-alkane crystals. The dye probe used was dimethyl-s-tetrazine and its perdeuterated derivative. We investigatedn-octane, perdeuteratedn-octane andn-hexane as host crystals. By comparing the experimentally observed hole-antihole splitting of the protonated and perdeuterated dye probe, all parameters, i.e. the tunneling splitting in the ground-and in the electronically excited state as well as the respective heights of the potential can be determined, assuming a threefold rotational symmetry axis. We found that matrix deuteration has a severe influence on the potential heights, which increase by a factor of two. With these parameters determined, many features of the complex relaxation behavior of the tunneling states can be qualitatively understood: We found Raman-type conversion processes inn-octane-h ₁₈, Orbach-type processes inn-octane-d ₁₈ and inn-hexane we found, in addition, a relaxation regime governed by a Direct process. The experimental activation energies as well as the cross-over temperatures are in satisfying agreement with current theories.     

Hindrance of the rotational relaxation in the excited singlet state of biphenyl and para-terphenyl in cooled solutions by methyl substituents

The measured fluorescence spectra of biphenyl (BP) and para-terphenyl (PTP) in solution reveal with decreasing temperature first an increasing structure and a slight red shift and below the glass transition a loss in structure and a strong blue shift. The effect is discussed using a torsional potential scheme in agreement with QCFF/PI calculations. Comparison of the experimental blue shifts with the results of CNDOS calculations suggest an incomplete hindrance of the relaxation process of the unsubstituted molecules. A nearly perfect hindrance could be detected for the tetra-methyl substituted BP and PTP molecules.     

Nuclear quadrupolar relaxation and the dynamics of pairs of atoms in liquids

We have developed a model calculation for the electrical field gradient correlation function on a probe atom in the liquid, c_EFG(t)=20(0)V₂₀(t)>. In this model, symmetry of the liquid is introduced explicitly and the distribution function for therelative coordinate r_i(t) between the probe atom and particle i is calculated using Smoluchowski's diffusion equation with a mean force potential Φ(r)=k_BT In g(r). The results for c_EFG(t) can be characterized by two correlation times, , the shorter one being responsible for the small values of R_Q in pure liquid metals, the longer one producing the increase of R_Q in alloys. Also good agreement is found with recent results for c_efg(t) from molecular dynamics studies.     

On the determination of the energy of activation of relaxation transitions in polymers by differential scanning calorimetry

The determination of the energy of activation (barrier height) of elementary events involved in relaxation (fluctuation) transitions in polymers from the temperature dependence of the specific heat is discussed. The dependence is derived by the method of differential scanning calorimetry. It is emphasized that the correct determination of the energy of activation must include the temperature variation of the barrier. The deviation of the preexponential in the Arrhenius temperature dependence from the value predicted theoretically demonstrates that the barrier does depend on temperature. Experimental data from which the realistic energy of activation of the α relaxation in polymers can be found are given.     

Effect of correlated temperature fluctuations on the phase dynamics in an ultrathin lubricant film

The melting of an ultrathin lubricant film at friction between atomically smooth surfaces is studied with allowance for fluctuations of its temperature, which are described by the Ornstein-Uhlenbeck process. The behavior of the most probable types of shear stresses arising in the lubricant is considered, and phase diagrams for second-and first-order phase transformations (the melting of an amorphous lubricant and that of a crystalline lubricant, respectively) are constructed. It is shown that, in the former case, lubricant temperature fluctuations lead to the formation of a stick-slip friction domain separating the domains of dry and sliding friction, which is typical of first-order transitions. In the latter case, three domains of stick-slip friction arise, which mark the transitions between dry friction and metastable and stable sliding friction. As the time of correlation of lubricant temperature fluctuations gets longer, the temperature of rubbing surfaces rises to the point where sliding friction sets in.     

Methodology for the measurement and analysis of relaxation times in proton imaging

Measurements of proton T1 and T2 were performed on GdCl3 solutions (20 less than T2 less than 500 msec, 90 less than T1 less than 1000 msec) on large-bore NMR imaging systems operating at 1.0T and 1.5T. CPMG multi-echo (ME), multiple saturation recovery (MSR) and modified fast inversion recovery (MFIR) pulse sequences as well as a sequence that combines and interleaves T1 and T2 weighted data acquisition (which we call "multiple saturation-recovery multiple-echo" (MSRME) were used. The relaxation data are compared to those obtained on a small bore NMR spectrometer operated at 1.5T. T1 and T2 values for the solutions were found to be the same within 10% for the two fields. Reproducibility of measurements of T1, T2 and the unnormalized spin density of the solutions was better than 5%. Systematic errors, amenable to correction through calibration, are noted in the imager T1 and T2 values. T1 and T2 values for some typical neural tissues at 1.5T and body tissue at 1.0T for human volunteers were obtained and are tabulated.     

Surface-driven instability and enhanced relaxation in the dynamics of a nonequilibrium interface

We determine the stability of a nonequilibrium interface between two coexisting solid phases in the presence of a weak external field. Starting at the coarsegrained (Cahn-Hilliard) level, we use the method of matched asymptotics to derive the macroscopic interfacial dynamics. We then show that the external field leads to an instability due to flux along the interface, in contrast with the more common Mullins-Sekerka type instability, which involves fluxes normal to the interface. We also find that the external field produces an important modification of the Gibbs-Thomson relation. With these results, we perform the linear stability analysis for an approximately flat interface. If the field is tangent to the interface, the modification of the Gibbs-Thomson relation is important and the interface is stabilized. If the field is normal to the interface, the surface flux is important, and the effect can be stabilizing or destabilizing, but the orientational dependence is opposite what would be obtained if the Mullins-Sekerka instability dominates. Numerical simulations are performed to study the effect of the surface current and are in agreement with our analytical results.     

基于车载被动差分光学吸收光谱技术的甲醛排放通量遥测研究

甲醛(HCHO)是大气中含量最为丰富的羰基化合物,广泛参与大气中的光化学反应,是一种重要的大气反应活性的指示剂以及城市大气气溶胶的前体物,在大气化学中扮演着重要的角色.本文初步探索了利用车载被动差分光学吸收光谱技术(differential optical absorption spectroscopy,DOAS)遥测...