Embedding beyond electrostatics-The role of wave function confinement

J Chem Phys. 2016 Sep 14;145(10):104102. doi: 10.1063/1.4962367.

Abstract

We study excited states of cholesterol in solution and show that, in this specific case, solute wave-function confinement is the main effect of the solvent. This is rationalized on the basis of the polarizable density embedding scheme, which in addition to polarizable embedding includes non-electrostatic repulsion that effectively confines the solute wave function to its cavity. We illustrate how the inclusion of non-electrostatic repulsion results in a successful identification of the intense π → π(∗) transition, which was not possible using an embedding method that only includes electrostatics. This underlines the importance of non-electrostatic repulsion in quantum-mechanical embedding-based methods.

MeSH terms

  • Cholesterol / chemistry*
  • Cholesterol / metabolism
  • Molecular Conformation
  • Molecular Dynamics Simulation
  • Quantum Theory*
  • Static Electricity*

Substances

  • Cholesterol