Rotational effects time dependence

The rotational relaxation time zK can be combined with time-dependent nuclear Overhauser effect (NOE) measurements to determine interproton... 

The electron-spin time-correlation functions of Eq. (56) were evaluated numerically by constructing an ensemble of trajectories containing the time dependence of the spin operators and spatial functions, in a manner independent of the validity of the Redfield limit for the rotational modulation of the static ZFS. Before inserting thus obtained electron-spin time-correlation functions into an equation closely related to Eq. (38), Abernathy and Sharp also discussed the effect of distortional/vibrational processes on the electron spin relaxation. They suggested that the electron spin relaxation could be described in terms of simple exponential decay rate constant Ts, expressed as a sum of a rotational and a distortional contribution ... 

The dependence of (20 MHz and 25° C) on is graphically represented in Pig. 3 for monoaqua Gd(III) complexes with different values of the rotational correlation times. The limiting effect of the residence lifetime is small for low molecular weight complexes (xf> = 50 100 ps) and detectable only when On the other hand, for slowly tumbling... 

The MacMichael viscometer is probably the most straightforward rotational viscometer. The outer cup rotates and the inner cylinder is suspended from a torsion wire. The drag on the inner cylinder is measured as degree of twist on the wire. Wires of different stiffness are available, and the maximum viscosity is ca 106 mPa-s. The shear rate range is limited, ca 2—12 s-1, but with modification, higher shear rates can be attained. The instrument is best suited for slow, time-dependent effects and low shear viscosities. 

Study of the charge transfer processes (step 3 above), free from the effects of mass transport, is possible by the use of transient techniques. In the transient techniques the interface at equilibrium is changed from an equilibrium state to a steady state characterized by a new potential difference A. The analysis of the time dependence of this transition is a basis of transient electrochemical techniques. We will discuss galvanostatic and potentiostatic transient techniques. For other techniques [e.g., alternating current (ac) and rotating electrodes], the reader is referred to references in the Further Reading list. 

FPA results obtained at different salt conditions may not be directly comparable because the fluorescence properties of 6-MI, including the lifetime (t), are salt dependent. The salt dependence of the FPA of a helix in a complex construct should thereby be normalized relative to the FPA of a short control duplex of the same sequence of the targeted helix to account for salt effects on the local environment of the 6-MI fluorophore. The normalization ratio, rnoml, can be calculated as the ratio between the apparent rotational correlation time, 9, of the constructs and the control duplex only, rnomi = construct/ control- is related to the rate of anisotropy decay, with larger 9 associated with higher anisotropy. If the basic Perrin equation for a sphere (Eq. (14.3)) is used to simplify calculation, then... 

The measurement of the polarization properties of light can be automated and improved by introducing a modulation of the polarization. Here a regular, time-dependent variation is introduced onto the optical properties of certain devices within either (or both) the PSG or PSA sections of the instrument. The modulation can be one of two types rotation of an optical element with fixed optical properties, or the modulation of the optical properties (retardation, for example) of an element with a fixed orientation. These are referred to as rotary modulators or field effect modulators, respectively. The latter name reflects the use of external fields (stress, electric or magnetic) to impart the modulation in these devices. In any case, a periodic oscillation is introduced into the signals that are measured that can effectively isolate specific optical properties in the sample. 

An issue that has been explored is how the relative distribution of charge and mass affect the viscosity of an ionic liquid. Kobrak and Sandalow [183] pointed out that ionic dynamics are sensitive to the distance between the centers of charge and mass. Where these centers are separated, ionic rotation is coupled to Coulomb interactions with neighboring ions where the centers of charge and mass are the same, rotational motion is, in the lowest order description, decoupled from an applied electric field. This is significant, because the Kerr effect experiments and simulation studies noted in Section III. A imply a separation of time scales for ionic libration (fast) and translation (slow) in ILs. Ions in which charge and mass centers are displaced can respond rapidly to an applied electric field via libration. Time-dependent electric fields are generated by the motion of ions in the liquid... 

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