J Chem Phys. 2013 Nov 28;139(20):204104. doi: 10.1063/1.4829836.

On the ground state calculation of a many-body system using a self-consistent basis and quasi-Monte Carlo: an application to water hexamer.

The Journal of chemical physics

Ionuţ Georgescu, Svetlana Jitomirskaya, Vladimir A Mandelshtam

PMID: 24289341 DOI: 10.1063/1.4829836

Abstract

Given a quantum many-body system, the Self-Consistent Phonons (SCP) method provides an optimal harmonic approximation by minimizing the free energy. In particular, the SCP estimate for the vibrational ground state (zero temperature) appears to be surprisingly accurate. We explore the possibility of going beyond the SCP approximation by considering the system Hamiltonian evaluated in the harmonic eigenbasis of the SCP Hamiltonian. It appears that the SCP ground state is already uncoupled to all singly- and doubly-excited basis functions. So, in order to improve the SCP result at least triply-excited states must be included, which then reduces the error in the ground state estimate substantially. For a multidimensional system two numerical challenges arise, namely, evaluation of the potential energy matrix elements in the harmonic basis, and handling and diagonalizing the resulting Hamiltonian matrix, whose size grows rapidly with the dimensionality of the system. Using the example of water hexamer we demonstrate that such calculation is feasible, i.e., constructing and diagonalizing the Hamiltonian matrix in a triply-excited SCP basis, without any additional assumptions or approximations. Our results indicate particularly that the ground state energy differences between different isomers (e.g., cage and prism) of water hexamer are already quite accurate within the SCP approximation.

Publication Types

• Journal Article