Self-cavity effect

Since the nineties of the last century, research groups around the world have explored the application of nanocapsules as nanoreactors, i.e. reaction vessels for chemical transformations, and the influence of different cavity effects." In this chapter the focus will mainly be on recent developments concerned with synthetic nanoreactors that can be obtained in a selective and controlled manner through the use of self-assembly principles and rational design, and on their application as catalytically active capsules for respective chemical reactions. For the sake of clarity, each specific type of nanoreactor will be discussed in a separate section. Particular types of nanocapsules to be reviewed include assemblies held together by hydrogen bonding, metal-ligand interactions and hydrophobic... 

Low-dimensional crystals such as epitaxial needles and solution-grown platelets of TPCOs act as a microscale gain medium. The self-cavity and self-waveguiding effects of these crystals result in ASE in the wavelength region of the fluorescence band where the self-absorption loss is minimized. Furthermore, the uniaxial orientation of the TPCO molecules in these low-dimensional crystals promotes the stimulated emission process and enhances the polarized ASE. 

Such coherent nonlinear effects may also induce gain losses by the self-focusing effect, destroying the desired mode properties of the optical cavity. A power threshold has been estimated by Yariv (1967)... 

A preliminary ejqieriment was peirformed in a small (7-f liter) cavity container placed in a relatively isotropic thermal flux of a conventional reactor. A gaseous (UF ) cavity was compared with a uniform dispersion of the above-mentioned fuel sheets (93.2% U-235). For equivalent reactivities, the U-23S mass in the fuel sheets was G% greater than in the gas, and this value is approximately the same as the thermal-flux self-shielding effect for such fuel sheets. 

Fig. 2.2 Self-Consistent Reaction Field (SCRF) model for the inclusion of solvent effects in semi-empirical calculations. The solvent is represented as an isotropic, polarizable continuum of macroscopic dielectric e. The solute occupies a spherical cavity of radius ru, and has a dipole moment of p,o. The molecular dipole induces an opposing dipole in the solvent medium, the magnitude of which is dependent on e.

In this contribution, we describe and illustrate the latest generalizations and developments[1]-[3] of a theory of recent formulation[4]-[6] for the study of chemical reactions in solution. This theory combines the powerful interpretive framework of Valence Bond (VB) theory [7] — so well known to chemists — with a dielectric continuum description of the solvent. The latter includes the quantization of the solvent electronic polarization[5, 6] and also accounts for nonequilibrium solvation effects. Compared to earlier, related efforts[4]-[6], [8]-[10], the theory [l]-[3] includes the boundary conditions on the solute cavity in a fashion related to that of Tomasi[ll] for equilibrium problems, and can be applied to reaction systems which require more than two VB states for their description, namely bimolecular Sjy2 reactions ],[8](b),[12],[13] X + RY XR + Y, acid ionizations[8](a),[14] HA +B —> A + HB+, and Menschutkin reactions[7](b), among other reactions. Compared to the various reaction field theories in use[ll],[15]-[21] (some of which are discussed in the present volume), the theory is distinguished by its quantization of the solvent electronic polarization (which in general leads to deviations from a Self-consistent limiting behavior), the inclusion of nonequilibrium solvation — so important for chemical reactions, and the VB perspective. Further historical perspective and discussion of connections to other work may be found in Ref.[l],... 

Acoustic cavitation (AC), formation of pulsating cavities in a fluid, occurs when a powerful ultrasound is applied to a non-viscous fluid. The cavities are formed when the variable acoustic pressure in the rarefaction phase exceeds the cohesive strength of the fluid. Under acoustic treatment (AT), cavities grow to resonance dimensions conditioned by frequency, amplitude of oscillations, stiffness properties and external conditions, and start to pulsate synchronously (self-consistently) with acoustic pressure in the medium. The cavities undergo significant strains (compared to their dimensions) and their size decreases under compression up to collapsing. This nonlinear behavior determines the active, destructional character of the cavities near which significant shear velocities, local pressure and temperature bursts occur in the fluid. Cavitation determines the specific character of acoustic treatment of the fluid and effects upon objects resident in the fluid, as well as all consequences of these effects. 

---