Anatoli A. Milischuk

Water dynamics in silica nanopores: The self-intermediate scattering functions

The dynamics of water molecules confined in approximately cylindrical silica nanopores is investigated using molecular simulation. The model systems are pores of diameter varying between 20 and 40 Å containing water at room temperature and at full hydration, prepared using grand canonical Monte Carlo simulation. Water dynamics in these systems is studied via molecular dynamics simulation. The results of the basic characterization of these systems have been reported in A. A. Milischuk and B. M. Ladanyi [J. Chem. Phys. 135, 174709 (2011)]. The main focus of the present study is the self-intermediate scattering function (ISF), F(S)(Q, t), of water hydrogens, the observable in quasi-elastic neutron scattering experiments. We investigate how F(S)(Q, t) depends on the pore diameter, the direction and magnitude of the momentum transfer Q, and the proximity of water molecules to the silica surface. We also study the contributions to F(S)(Q, t) from rotational and translational motions of water molecules and the extent of rotation-translation coupling present in F(S)(Q, t). We find that F(S)(Q, t) depends strongly on the pore diameter and that this dependence is due mainly to the contributions to the ISF from water translational motion and can be attributed to the decreased mobility of water molecules near the silica surface. The relaxation rate depends on the direction of Q and is faster for Q in the axial than in the radial direction. As the magnitude of Q increases, this difference diminishes but does not disappear. We find that its source is mainly the anisotropy in translational diffusion at low Q and in molecular reorientation at higher Q values.

Equilibrium solvation in quadrupolar solvents

We present a microscopic theory of equilibrium solvation in solvents with zero dipole moment and nonzero quadrupole moment (quadrupolar solvents). The theory is formulated in terms of autocorrelation functions of the quadrupolar polarization (structure factors). It can be therefore applied to an arbitrary dense quadrupolar solvent for which the structure factors are defined. We formulate a simple analytical perturbation treatment for the structure factors. The solute is described by coordinates, radii, and partial charges of constituent atoms. The theory is tested on Monte Carlo simulations of solvation in model quadrupolar solvents. It is also applied to the calculation of the activation barrier of electron transfer reactions in a cleft-shaped donor-bridge-acceptor complex dissolved in benzene with the structure factors of quadrupolar polarization obtained from molecular-dynamics simulations.

On the validity of dielectric continuum models in application to solvation in molecular solvents

We report Monte Carlo simulations of solvation of a point dipole in dipolar–quadrupolar solvents of varying dipole moment and axial quadrupole. The simulations are carried out to test the prediction of dielectric solvation models of a monotonic increase of the absolute value of the solvation chemical potential |μp| with the solvent dielectric constant e. Dielectric constants are obtained from pure liquid simulations carried out for each solvent used in solvation simulations. A raising dependence of |μp| on e, in qualitative agreement with dielectric solvation models, is seen when the solvent dipole moment is varied at constant solvent quadrupole. An increase in the axial quadrupole at constant solvent dipole reduces the dielectric constant at the same time leading to higher |μp| values. The simulations and dielectric models thus give the opposite dependence on the solvent quadrupole for any solvent dipole. We also show that for solvation in dipolar–quadrupolar solvents the saturation limit |μp|→const at e...

Non-Condon theory of nonadiabatic electron transfer reactions in V-shaped donor–bridge–acceptor complexes

The rate of nonadiabatic long-distance electron transfer (ET) is derived for the direct and superexchange electronic coupling between the donor and acceptor. The model takes into account a non-Condon thermal modulation of the electronic coupling through the interaction of the system transition dipoles with the polarization fluctuations of the solvent. Going from a linear donor–bridge–acceptor complexes to a bent, V-shaped geometry lowers the system symmetry resulting in several novel properties of the ET matrix element based on the fact that permanent and transition dipoles in the system are not polarized along the direction of ET. The effective ET matrix element HET gains two zeros as a function of the donor–acceptor vertical energy gap. The positions of zeros of HET depend on the sign relations between the donor–bridge and bridge–acceptor electronic couplings and corresponding transition dipoles. The ET matrix element becomes dependent on solvent through the solvent refractive index and the inhomogeneou...

Quadrupolar solvatochromism: 4-amino-phthalimide in toluene

We present calculations of the temperature dependence of the solvent reorganization energy of 4-amino-phthalimide chromophore in quadrupolar toluene. The reorganization energy is a sum of the contributions from quadrupolar and induction solvation. We employ several calculation formalisms in order to evaluate their performance against the experiment. The point-dipole and full atomic distributions of solute charge are compared to show that the point-dipole approximation works well for this chromophore. We also show that most of the reorganization entropy comes from the quadrupolar response. Induction solvation amounts to about 10% of the entropy. Both the reorganization energy and the reorganization entropy are greatly affected by the local solute-solvent density profile (density reorganization) which contributes about half of their values. The induction reorganization energy is strongly affected by the microscopic, nonlocal nature of the density fluctuations of the solvent around the solute.

Self-intermediate scattering function analysis of supercooled water confined in hydrophilic silica nanopores

We study the temperature dependence of the self-intermediate scattering function for supercooled water confined in hydrophilic silica nanopores. We simulate the simple point charge/extended model of water confined to pores of radii 20 Å, 30 Å, and 40 Å over a temperature range of 210 K to 250 K. First, we examine the temperature dependence of the structure of the water and find that there is layering next to the pore surface for all temperatures and diameters. However, there exists a region in the center of the pore where the density is nearly constant. Using the density profile, we divide confined water into different regions and compare the dynamics of the water molecules that start in these regions. To this end, we examine the mean-squared displacement and the self-intermediate scattering functions for the water hydrogens, which would allow one to connect our results with quasi-elastic neutron scattering experiments. We examine the dependence of the self-intermediate scattering function on the magnitude and direction of the wavevector, as well as the proximity to the silica surface. We also examine the rotational-translational decoupling. We find that the anisotropy of the dynamics and the rotational-translational decoupling is weakly temperature dependent.