Fast geometry optimizationin self‐cosistent reaction field computations on solvated molecules

Abstract

Abstract The free energy gradient or Hessian of a molecule interacting with a liquid represented by a dielectric continuum is derived in the self‐consistent reaction field formalism. An ellipsoidal approximation of the cavity is proposed with an algorithm to automatically define the ellipsoid from the nuclear coordinates of the atoms. With this approximation, geometry optimization of the solvated molecule becomes very fast. This method has been implemented in some standard ab initio or semiempirical computational codes. As a first test of the method, full geometry optimization of formamide in a high dielectric constant medium reveals that the CPU time needed for one optimization cycle is less than 3% longer for a solvated species than for the corresponding free molecule.