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 Schrödinger 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.

arXiv comment14 pages, 3 figures, 2 tables

References in corpus (10)

• The Open Catalyst 2020 (OC20) Dataset and Community Challenges
• Reliable and Practical Computational Prediction of Molecular Crystal Polymorphs
• Interactions between Large Molecules: Puzzle for Reference Quantum-Mechanical Methods
• Many-body quantum chemistry for the electron gas: convergent perturbative theories
• Assessing density functionals using many body theory for hybrid perovskites
• Low rank factorization of the Coulomb integrals for periodic coupled cluster theory
• Combining Machine Learning and Many-Body Calculations: Coverage-Dependent Adsorption of CO on Rh(111)
• Averting the infrared catastrophe in the gold standard of quantum chemistry
• Linear-scaling local natural orbital CCSD(T) approach for open-shell systems: algorithm, benchmarks, and large-scale applications
• Focal-point approach with pair-specific cusp correction for coupled-cluster theory