Torsional path integral Monte Carlo method for calculating the absolute quantum free energy of large molecules

Abstract

A new technique for evaluating the absolute free energy of large molecules is presented. Quantum-mechanical contributions to the intramolecular torsions are included via the torsional path integral Monte Carlo (TPIMC) technique. Importance sampling schemes based on uncoupled free rotors and harmonic oscillators facilitate the use of the TPIMC technique for the direct evaluation of quantum partition functions. Absolute free energies are calculated for the molecules ethane, n-butane, n-octane, and enkephalin, and quantum contributions are found to be significant. Comparison of the TPIMC technique with the harmonic oscillator approximation and a variational technique is performed for the ethane molecule. For all molecules, the quantum contributions to free energy are found to be significant but slightly smaller than the quantum contributions to internal energy.