Temperature and Density Effects on an SN2 Reaction in Supercritical Water

Ab-initio Study of NMR Chemical Shifts of Water Under Normal and Supercritical Conditions

“…It can also be formulated as the second derivative of the energy with respect to the nuclear magnetic moment and the external magnetic field, Equation (2).…”

A Compressible Continuum Model Study of the Chloride plus Methyl Chloride Reaction in Supercritical Water

“…18,42,43 Thus, the parameters used to model this system have been chosen to correspond to the simulated system.…”

“…The solute cavity is taken to be the solvent accessible surface (probe radius of 1.4 Å) created by the interlocking atomic spheres whose radii are taken as follows: the reaction path-dependent Cl radii are taken directly from the Lennard-Jones values used in the simulation, 42 41 also considered a second radius set, R′, which was optimized to accurately predict the experimental solvation free energy of an isolated chloride ion in water under ambient conditions. These authors compared the relative free energies of solvation along the reaction path computed from the IC model with each of the two radius sets in water under ambient conditions, i.e., s ) 80, with those computed from simulation under the same conditions.…”

A Continuum Solvation Model Including Electrostriction: Application to the Anisole Hydrolysis Reaction in Supercritical Water

“…3,13 This variation in reaction process with pressure is known to be tied to the large variation in SCW's density, and thus its dielectric properties, with pressure in this regime. [2][3][4][14][15][16] For example, at 380°C, the dielectric constant of water varies from ) 2 at P ) 21 MPa to ) 14 at P ) 47 MPa. 17 This extreme variation in density-dependent solvent properties with moderate changes in pressure is typical of SCF's in the region of phase diagram where their isothermal compressibility is large.…”