Relaxation (NMR)

About: Relaxation (NMR) is a research topic. Over the lifetime, 29342 publications have been published within this topic receiving 689851 citations.

Dielectric relaxation of aqueous NaCl solutions

Abstract: The complex dielectric permittivity of aqueous sodium chloride solutions has been determined in the frequency range 0.2 ≤ v(GHz) ≤ 20 with a commercial dielectric measurement system based on a vector network analyzer. NaCl solutions 0.1 ≤ m (mol kg-1) ≤ 5 (mass fraction 0.005 ≤ w ≤ 0.23) were investigated at 5, 20, 25, and 35°C. An improved calibration procedure of the dielectric measurement system for conducting samples was developed. The complex permittivity spectra have been represented by a Cole-Cole relaxation time distribution. Where possible, the obtained fitting parameters, static permittivity ∈ and relaxation time τ, and distribution parameter a, are compared with literature data to assess the performance of the instrument, which was found to be comparable to that of time domain and waveguide systems. Effective solvation numbers were deduced from the effect of NaCl concentration on ∈. The data suggest that in addition to the irrotational bonding of water molecules by Na+ ions, kinetic depolarization under slip boundary conditions determines the solution permittivity. A three-state model is proposed to describe the concentration dependence of τ. © Copyright 1999 by the American Chemical Society.

Single Pyramid Magnets: Dy5 Pyramids with Slow Magnetic Relaxation to 40 K

Abstract: Single-molecule magnets: A square-pyramidal pentametallic dysprosium cluster was synthesized and showed slow magnetic relaxation at temperatures as high as 40 K. The thermal energy barrier to relaxation of magnetization of this single-molecule magnet was found at a temperature of 530 K and is the largest yet observed for any d- or f-block cluster compound.

Third-order nonlinear time domain probes of solvation dynamics

Abstract: Several closely related third‐order nonlinear time‐resolved spectroscopic techniques, pump/probe transient absorption, transient grating, and three pulse stimulated photon echo peak shift measurements, are investigated theoretically and experimentally. It is shown in detail, through the consideration of response functions and numerical simulations including both finite pulse durations and detuning from exact resonance, how the solvation dynamics are manifested in these third‐order nonlinear time‐resolved spectroscopies. It is shown that the three pulse stimulated photon echo peak shift measurement and the transient grating measurement can give accurate dynamical information, whereas transient absorption may not be a reliable technique for a study of solvation dynamics in some cases. The contribution of very slow or static (inhomogeneous) components to the dynamics, however, can only be obtained from the three pulse echo peak shift measurements. Comprehensive experimental measurements are presented to illustrate and corroborate the calculations. We show that it is possible to separate the intramolecular vibrational and solvent contributions to the dephasing (or optical lineshape). Furthermore it is shown that the solvation of polar solutes in polar protic solvents has rather universal characteristics. The initial ultrafast process, usually identified as an inertial response of solvent molecules, occurs on a ∼100 fs time scale, and is essentially identical in methanol, ethanol, and butanol. The amplitude of this ultrafast component does, however, decrease with increasing alcohol size in 1‐alkanols. The diffusive (≳0.5 ps) regime of the solvation process shows a strong solvent dependence, and may be described satisfactorily by dielectric relaxation theories.

Specific-Heat Spectroscopy of the Glass Transition

Abstract: The glass transition has historically been viewed as an anomaly involving the specific heat of supercooled liquids. It is also associated with a divergence of the relaxation times for liquid rearrangements. We have developed a new spectroscopy to study the frequency dependence of the specific heat of liquids which connects these two approaches. We report measurements as a function of temperature of the distribution of relaxation times which are directly responsible for the glass transition in glycerol.

An air-stable Dy(iii) single-ion magnet with high anisotropy barrier and blocking temperature

Abstract: Herein we report air-stable Dy(III) and Er(III) single-ion magnets (SIMs) with pseudo-D5h symmetry, synthesized from a sterically encumbered phosphonamide, tBuPO(NHiPr)2, where the Dy(III)-SIM exhibits a magnetization blocking (TB) up to 12 K, defined from the maxima of the zero-field cooled magnetization curve, with an anisotropy barrier (Ueff) as high as 735.4 K. The Dy(III)-SIM exhibits a magnetic hysteresis up to 12 K (30 K) with a large coercivity of ∼0.9 T (∼1.5 T) at a sweep rate of ∼0.0018 T s−1 (0.02 T s−1). These high values combined with persistent stability under ambient conditions, render this system as one of the best-characterized SIMs. Ab initio calculations have been used to establish the connection between the higher-order symmetry of the molecule and the quenching of quantum tunnelling of magnetization (QTM) effects. The relaxation of magnetization is observed via the second excited Kramers doublet owing to pseudo-high-order symmetry, which quenches the QTM. This study highlights fine-tuning of symmetry around the lanthanide ion to obtain new-generation SIMs and offers further scope for pushing the limits of Ueff and TB using this approach.