A path integral ground state approach for asymmetric top rotors with nuclear spin symmetry: Application to water chains

Abstract

A path integral ground state (PIGS) approach for the simulation of asymmetric top rotors is presented. The method is based on Monte Carlo sampling of angular degrees of freedom. A symmetry-adapted rotational density matrix is used to account for nuclear spin statistics. To illustrate the method, ground-state properties of collections of para-water molecules confined to a one-dimensional lattice are computed. Those include energetic and structural observables. An advantage of the PIGS method is that expectation values can be obtained directly since the square of the wavefunction is sampled during a simulation. To benchmark the method, ground state energies and orientational distributions are computed using exact diagonalization for a single para-water molecule in an external field using a finite basis of symmetric top eigenfunctions. Benchmark results are also provided for N = 2 para-water molecules pinned to lattice sites at various distances to sample the crossover from hydrogen bonding to the dipole-dipole interaction regime. Excellent agreement between the PIGS results and the finite basis set calculations is observed. A thorough analysis of the convergence in terms of the imaginary time propagation length and systematic Trotter error is performed. The PIGS approach is then applied to a chain of N = 11 water molecules, and an equation of state is constructed in terms of the intermolecular separation. Ordering effects are also studied, and a transition between hydrogen bonding to dipole-dipole alignment is observed. The method is scalable and can also be applied in higher dimensions.