Work

Ligand Many-Body Expansion as a General Approach for Accelerating Transition Metal Complex Discovery

Year: 2024

Type: article

Abstract: Methods that accelerate the evaluation of molecular properties are essential for chemical discovery. While some degree of ligand additivity has been established for transition metal complexes, it is underutilized in asymmetric complexes, such as the square pyramidal coordination geometries highly relevant to catalysis. To develop predictive methods beyond simple additivity, we apply a many-body expansion to octahedral and square pyramidal complexes and introduce a correction based on adjacent ligands (i.e., the cis interaction model). We first test the cis interaction model on adiabatic spin-splitting energies of octahedral Fe(II) complexes, predicting DFT-calculated values of unseen binary complexes to within an average error of 1.4 kcal/mol. Uncertainty analysis reveals the optimal basis, comprising the homoleptic and mer symmetric complexes. We next show that the cis model (i.e., the cis interaction model solved for the optimal basis) infers both DFT- and CCSD(T)-calculated model catalytic reaction energies to within 1 kcal/mol on average. The cis model predicts low-symmetry complexes with reaction energies outside the range of binary complex reaction energies. We observe that trans interactions are unnecessary for most monodentate systems but can be important for some combinations of ligands, such as complexes containing a mixture of bidentate and monodentate ligands. Finally, we demonstrate that the cis model may be combined with Δ-learning to predict CCSD(T) reaction energies from exhaustively calculated DFT reaction energies and the same fraction of CCSD(T) reaction energies needed for the cis model, achieving around 30% of the error from using the CCSD(T) reaction energies in the cis model alone.

Source: Journal of Chemical Information and Modeling

DOI: 10.1021/acs.jcim.4c01728

Authors: Daniel B. K. Chu, David A. González-Narváez, Ralf Meyer, Aditya Nandy, Heather J. Kulik

Institution: Massachusetts Institute of Technology

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, U.S. Department of Energy, Basic Energy Sciences, Department of Energy National Nuclear Security Administration Laboratory Residency Graduate Fellowship

Awards: Graduate Research Fellowship Program, G6016308158, Graduate Research Fellowship Program (GRFP), G7821822901, 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.