Reversibly intrinsic systems

Real organic thermochromism - reversibly intrinsic systems... 

Since many systems of interest in chemistry have intrinsic multiple time scales it is important to use integrators that deal efficiently with the multiple time scale problem. Since our multiple time step algorithm, the so-called reversible Reference System Propagator Algorithm (r-RESPA) [17, 24, 18, 26] is time reversible and symplectic, they are very useful in combination with HMC for constant temperature simulations of large protein systems. 

A technically more appropriate approach is to separate reversible organic thermochromism into intrinsic systems, where heat is the sole cause of the colour change, from indirect systems, in which the colour variation involves changes in... 

A technically more appropriate approach would be to diversify the reversible organic thermochromism of intrinsic systems, in which heat is the only factor influencing the colour change, from the indirect systems in which the colour change is induced by the heat that affects the surroundings of the chromophore (Burkinshaw et al., 1999). 

There are also reactions in which hydride is transferred from carbon. The carbon-hydrogen bond has little intrinsic tendency to act as a hydride donor, so especially favorable circumstances are required to promote this reactivity. Frequently these reactions proceed through a cyclic TS in which a new C—H bond is formed simultaneously with the C-H cleavage. Hydride transfer is facilitated by high electron density at the carbon atom. Aluminum alkoxides catalyze transfer of hydride from an alcohol to a ketone. This is generally an equilibrium process and the reaction can be driven to completion if the ketone is removed from the system, by, e.g., distillation, in a process known as the Meerwein-Pondorff-Verley reduction,189 The reverse reaction in which the ketone is used in excess is called the Oppenauer oxidation. 

The building blocks of supramolecular systems are held together by intramolecular interactions and these systems are reversible. This intrinsic property is not only a consequence of the more labile interactions within supermolecules, compared to covalent bonds in molecules, but reversibility is essential for the function expressed by supramolecular systems. Kinetics can never be inferred from thermodynamic studies. For example, the knowledge of a host-guest equilibrium constant does not... 

The passage from one control to the other is pictured in Figure 2.5 for the cathodic peak potential and the peak width as a function of the scan rate and of the intrinsic parameters of the system. We note that increasing the scan rate tends to move the kinetic control from the follow-up reaction to the electron transfer step. It thus appears that the overall reaction may well be under the kinetic control of electron transfer, even if this is intrinsically fast, provided that the follow-up reaction is irreversible and fast. The reason is that the follow-up reaction prevents the reverse electron transfer from operating, thus making the forward electron transfer the rate-determining step. 

Systems and molecules showing intrinsic reversible thermochromism can be classified as follows ... 

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