Understanding Discrepancies of Wavefunction Theories for Large Molecules

Abstract

Quantum mechanical many-electron calculations can predict properties of atoms, molecules and even complex materials. The employed computational methods play a quintessential role in many scientifically and technologically relevant research fields. However, a question of paramount importance is whether approximations aimed at reducing the computational complexity for solving the many-electron Schr\"odinger equation, are accurate enough. Here, we investigate recently reported discrepancies of noncovalent interaction energies for large molecules predicted by two of the most widely-trusted many-electron theories: diffusion quantum Monte Carlo and coupled-cluster theory. We are able to unequivocally pin down the source of the puzzling discrepancies and present modifications to widely-used coupled-cluster methods needed for more accurate noncovalent interaction energies of large molecules on the hundred-atom scale. This enhances the reliability of predictions from quantum mechanical many-electron theories across a wide range of critical applications, including drug design, catalysis, and the innovation of new functional materials, such as those for renewable energy technologies.