Torsional path-integral Monte Carlo method for the quantum simulation of molecular systems

A molecular application is introduced for calculating quantum statistical mechanical expectation values of large molecules at non-zero temperatures. The torsional path integral Monte Carlo (PIMC) technique applies an uncoupled winding number formalism to the torsional degrees of freedom in molecular systems. The internal energy of the molecules ethane, n-butane, n-octane, and enkephalin are calculated at standard temperature using the torsional PIMC technique and compared to the expectation values obtained using the harmonic oscillator approximation and a variational technique. All studied molecules exhibited signiftcant quantum mechanical contributions to their internal energy expectation values according to the torsional PIMC technique. The harmonic oscillator approximation approach to calculating the internal energy performs well for the molecules presented in this study but is limited by its neglect of both anharmonicity effects and the potential coupling of intramolecular torsions