DFT-Based Multireference Diagnostics in the Solid State: Application to Metal-Organic Frameworks | JoVE Visualize

Area of Science:

Computational Chemistry
Materials Science
Solid-State Physics

Background:

Accurate electronic structure description of many-body systems often requires high-level multireference (MR) methods when single-determinant approximations fail.
Existing MR diagnostics, used to quantify static correlation, are predominantly developed for molecular systems and vary significantly in computational cost.
The application of these diagnostics to solid-state systems remains largely unexplored.

Purpose of the Study:

To introduce and validate low-cost multireference diagnostics for solid-state systems.
To assess the applicability of finite-temperature DFT-based MR diagnostics to metal-organic frameworks (MOFs) and their molecular derivatives.
To establish a correlation between the MR character of MOFs and their molecular counterparts for efficient computational screening.

Main Methods:

Application of fractional occupation number diagnostics derived from finite-temperature density-functional theory (DFT).
Utilized a series of closed-shell metal-organic frameworks (MOFs) and their corresponding molecular derivatives as model systems.
Compared the MR character (magnitude and spatial distribution) between the solid MOF systems and their molecular analogues.

Main Results:

Demonstrated the successful application of DFT-based MR diagnostics to solid-state MOF systems for the first time.
Established that the MR character of MOFs correlates well with that of their molecular derivatives.
Showcased that molecular derivatives can be computed significantly more affordably than the full MOF, while retaining comparable MR information.

Conclusions:

Low-cost MR diagnostics are effective for analyzing the electronic structure of solid-state materials, specifically MOFs.
The MR character of MOFs can be reliably predicted using their more computationally accessible molecular derivatives.
This approach facilitates accurate and efficient high-throughput screening of MOFs and other porous solids for desired electronic properties.