Unveiling the Finite Temperature Physics of Hydrogen Chains via Auxiliary Field Quantum Monte Carlo

Journal Article · 25 May 2020 · Journal of Chemical Theory and Computation

DOI: https://doi.org/10.1021/acs.jctc.0c00288 · OSTI ID:1709103

Liu, Yuan  ^[1]; Shen, Tong ^[1]; Zhang, Hang ^[2]; Rubenstein, Brenda ^[1]

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1. Brown Univ., Providence, RI (United States)
2. Princeton Univ., NJ (United States)

The ability to accurately predict the finite temperature properties and phase diagrams of realistic quantum solids is central to uncovering new phases and engineering materials with novel properties ripe for device applications. Nonetheless, there remain comparatively few many-body techniques capable of elucidating the finite temperature physics of solids from first principles. Here, we take a significant step toward developing such a technique by generalizing our previous, exact fully ab initio finite temperature Auxiliary Field Quantum Monte Carlo (FT-AFQMC) method to model periodic solids and employing it to uncover the finite temperature physics of periodic hydrogen chains. Our chains’ unit cells consist of 10 hydrogen atoms modeled in a minimal basis, and we sample 5 k-points from the first Brillouin zone to arrive at a supercell consisting of 50 orbitals and 50 electrons. Based upon our calculations of these chains’ many-body energies, free energies, entropies, heat capacities, double and natural occupancies, and charge and spin correlation functions, we outline their metal–insulator and magnetic ordering as a function of both H–H bond distance and temperature. At low temperatures approaching the ground state, we observe both metal–insulator and ferromagnetic–antiferromagnetic crossovers at bond lengths between 0.5 and 0.75 Å. We then demonstrate how this low-temperature ordering evolves into a metallic phase with decreasing magnetic order at higher temperatures. In order to contextualize our results, we compare the features we observe to those previously seen in one-dimensional, half-filled Hubbard models at finite temperature and in ground state hydrogen chains. Interestingly, we identify signatures of the Pomeranchuk effect in hydrogen chains for the first time and show that spin and charge excitations that typically arise at distinct temperatures in the Hubbard model are indistinguishably coupled in these systems. Beyond qualitatively revealing the many-body phase behavior of hydrogen chains in a numerically exact manner without invoking the phaseless approximation, our efforts shed light on the further theoretical developments that will be required to construct the phase diagrams of the more complex transition metal, lanthanide, and actinide solids of longstanding interest to physicists.

• Research Organization: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
• Grant/Contract Number: AC05-00OR22725
• OSTI ID: 1709103
• Journal Information: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 7 Vol. 16; ISSN 1549-9618
• Publisher: American Chemical SocietyCopyright Statement
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hamiltonians
energy
hydrogen
internal energy
quantum mechanics