Tuesday, June 13, 2017

Abstract-Terahertz absorption of lysozyme in solution

Absorption of radiation by solution is described by the solution dielectric constant and can be viewed as a specific application of the dielectric theory of solutions. For ideal solutions, the dielectric boundary value problem separates the polar response into the polarization of the void in the liquid created by the solute and the response of the solute dipole. In the case of a protein as a solute, its nuclear dynamics do not project on significant fluctuations of the dipole moment in the terahertz domain of frequencies and the protein dipole can be viewed as dynamically frozen. Absorption of radiation then reflects the interfacial polarization. Here we apply an analytical theory and computer simulation to absorption of radiation by ideal solutions of lysozyme. Comparison with experiment shows that Maxwell electrostatics fails to describe the polarization of the protein-water interface and the "Lorentz void", which does not anticipate polarization of the solute void by the external field (no surface charges), better represents the data. An analytical theory for the slope of the solution absorption against the volume fraction of the solute is formulated in terms of the cavity field response function. It is calculated from molecular dynamics simulations in good agreement with experiment. The protein hydration shell emerges as a separate sub-ensemble, which collectively is not described by the standard electrostatics of dielectrics.

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