DFT-Based Multireference Diagnostics in the Solid State: Application to Metal–Organic Frameworks
Year: 2022
Type: article
Abstract: When a many-body wave function of a system cannot be captured by a single determinant, high-level multireference (MR) methods are required to properly explain its electronic structure. MR diagnostics to estimate the magnitude of such static correlation have been primarily developed for molecular systems and range from low in computational cost to as costly as the full MR calculation itself. We report the first application of low-cost MR diagnostics based on the fractional occupation number calculated with finite-temperature DFT to solid-state systems. To compare the behavior of the diagnostics on solids and molecules, we select metal-organic frameworks (MOFs) as model materials because their reticular nature provides an intuitive way to identify molecular derivatives. On a series of closed-shell MOFs, we demonstrate that the DFT-based MR diagnostics are equally applicable to solids as to their molecular derivatives. The magnitude and spatial distribution of the MR character of a MOF are found to have a good correlation with those of its molecular derivatives, which can be calculated much more affordably in comparison to those of the full MOF. The additivity of MR character discussed here suggests the set of molecular derivatives to be a good representation of a MOF for both MR detection and ultimately for MR corrections, facilitating accurate and efficient high-throughput screening of MOFs and other porous solids.
Institution: Massachusetts Institute of Technology
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
Awards: Graduate Research Fellowship Program, G4475768270, S2I2: Impl: The Molecular Sciences Software Institute, G5662436926, G6191928423, WE PROPOSE THE CREATION OF A SINGLE-DISCIPLINE CENTER (SDC) FOR THE EXASCALE SIMULATION OF MATERIALS IN
HYPERSONIC FLOW ENVIRONMENTS. OUR OBJECTIVES ARE AS FOLLOWS. FIRST, WE TARGET A SIGNIFICANT ADVANCE IN THE
ABILITY TO PREDICT THE DEGRADATION (OXIDATION AND MELTING) OF COMPLEX (DISORDERED AND MULTI-COMPONENT) MATERIALS
UNDER EXTREME LOADING, INACCESSIBLE TO DIRECT EXPERIMENTAL OBSERVATION. THIS APPLICATION REPRESENTS A
TECHNOLOGY DOMAIN OF INTENSE CURRENT INTEREST, AND HAS CLEAR EXTENSIONS TO A MUCH WIDER CLASS OF PROBLEMS—
I.E., THOSE INVOLVING MATERIAL INTERFACES IN EXTREME ENVIRONMENTS. INDEED, INTERFACES ARE CRUCIAL TO OUR ABILITY
TO UNDERSTAND, ENGINEER, AND CONTROL MATERIAL BEHAVIOR. YET THE PREDICTIVE SIMULATION OF INTERFACE PROPERTIES
AND THEIR IMPACT REMAINS EXTREMELY CHALLENGING. CAPTURING THE IMPACT OF INTERFACES REQUIRES RESOLVING INTERFACIAL
ATOMIC STRUCTURE AND THUS APPEALING TO FIRST PRINCIPLES (I.E., QUANTUM MECHANICAL) SIMULATIONS; AT THE
SAME TIME, INTERFACIAL STRUCTURES ARE AFFECTED BY CONDITIONS (E.G., THERMAL, MECHANICAL, AND CHEMICAL LOADING)
AT THE ENGINEERING SCALE. THIS PROBLEM THUS PRESENTS AN ENORMOUS AND FUNDAMENTAL MULTISCALE SIMULATION
CHALLENGE, WITH MYRIAD APPLICATIONS—TO HYPERSONICS AND FAR BEYOND.
OpenAlex ID: W4312094621