Molecular dynamics simulation of cooling: Heat transfer from a photoexcited peptide to the solvent

Abstract

A systematic molecular dynamics (MD) simulation study of the photoinduced heat transfer from the model peptide N-methylacetamide (NMA) to various solvents is presented, which considers four types of solvent (water, dimethyl sulfoxide, chloroform, and carbon tetrachloride), and in total 24 different force field models for these solvents. To initiate nonstationary energy flow, an initial temperature jump of NMA is assumed and nonequilibrium MD simulations are performed. As expected from simple theoretical models of heat transfer, the cooling process is proportional to the heat capacity C(V) and--to some extent--to the viscosity eta of the solvent. The complex interplay of Coulomb and Lennard-Jones interactions is studied by scaling these interaction energies. The study reveals that realistic changes (< or approximately 10%) of the Lennard-Jones and Coulomb parameters do not change the cooling time considerably. Including polarizibility, on the other hand, appears to enhance the energy dissipation. Moreover, the solvent's internal degrees of freedom may significantly participate in the heat transfer. This is less so for water, which possesses only three high-frequency vibrational modes, but certainly so for the larger solvent molecules dimethyl sulfoxide and chloroform, which possess several low-frequency vibrational modes. For water, the simulated cooling rate is in excellent agreement with experiment, while only qualitative agreement (up to a factor of 2) is found for the other considered solvents. The importance of the force field model and quantum-mechanical effects to correctly describe the cooling process is discussed in some detail.