Dr. Richard Henchman: New Publication
A molecule’s intramolecular entropy contributes to numerous properties such as its conformation, solubility, binding, and reactivity. However, it is a difficult quantity to determine. During his Humboldt Fellowship at the Heidelberg Institute of Theoretical Studies, Richard Henchman developed a new method to calculate intramolecular entropy from the eigenvalues of the mass-weighted force covariance matrix, exploiting the intuitive link between larger forces and lower entropy.
The method's performance for a series of linear hydrocarbons is presented in the accompanying figure. It is more accurate than entropies derived using coordinate covariance, more efficient than the robust but demanding method of thermodynamic integration, and agrees well with experiment. This improved capability should make intramolecular entropy a more accessible and useful quantity.
Macromolecular Entropy Can Be Accurately Computed from Force, Ulf Hensen, Frauke Gräter, and Richard H. Henchman, J. Chem. Theory Comput., 2014, 10, 4777-4781.