Supplementary Research Data for "Decomposition of magnetic coupling in μ-oxo-bridged metal complexes"

Overview This repository contains all computational data required to reproduce the results presented in the publication: “Decomposition of magnetic coupling in μ-oxo-bridged metal complexes” The dataset includes complete input, output, and structure files for all electronic-structure calculations discussed in the main text and Supporting Information. These data cover dinuclear copper, nickel, and iron complexes and comprise broken-symmetry DFT (BS-DFT), CASSCF, and Difference Dedicated Configuration Interaction (DDCI) calculations, as well as geometry optimizations and systematic angle/dihedral scans. All calculations were performed with ORCA v5.0.3, and the provided files are organized to allow direct reproduction of all reported results. Repository Structure > Geometry-Opt > BS-DFT > CASSCF > Angle-Scan > Dieder-Scan Each directory is described in detail below. 1. Geometry-Optimizations This folder contains all files related to the broken-symmetry DFT geometry optimizations of the dinuclear complexes. Contents .inp – ORCA input files .out – ORCA output files .xyz – optimized molecular geometries Details Geometry optimizations were performed using the PBE0, B3LYP, and TPSSh functionals. Structural differences between the optimized geometries are discussed in detail in the Supporting Information. All subsequent calculations (BS-DFT single points, CASSCF, DDCI, scans) use the PBE0-optimized geometries. 2. BS-DFT This folder contains single-point broken-symmetry DFT calculations used as reference throughout the manuscript. Contents .inp – single-point BS-DFT input files .out – corresponding output files Details Calculations were performed with the PBE0, TPSS0, and TPSSh hybrid functionals. All output files report magnetic coupling constants extracted using projection formulas by Ruiz, Noodleman, and Yamaguchi. The Yamaguchi projection was used as the primary reference in the main text. 3. CASSCF-DDCI This directory contains all state-averaged CASSCF and DDCI calculations, including both minimal and extended active spaces. Systems and Active Spaces Copper complex Minimal: CAS(2,2) Extended: CAS(8,5) Nickel complex Minimal: CAS(4,4) Extended: CAS(10,7) Iron complex Minimal: CAS(8,8) Extended: CAS(14,11) Methods CASSCF DDCI1 DDCI2 DDCI3 (where computationally feasible) Analysis Files Each complex directory contains an Analysis.odp file, which documents the full Valence / Intermediate Effective Hamiltonian (VIEH/IEH) analysis, including: spin-state energies, configuration interaction coefficients, orbital energies, extraction of effective parameters for all available magnetic coupling pathways. These files allow a step-by-step reproduction of all decoupling analyses reported in the manuscript. 4. Angle-Dihedral-Scans This folder contains all calculations associated with geometric distortion scans, discussed in Section 4.3 of the main text. Scans Performed M–O–M bond angle scans M–O–M–N dihedral scans Details All scan points were generated from the PBE0-optimized geometries. Internal coordinates exported by ORCA were explicitly loaded in each input file. Angles were varied in 1° increments, dihedrals in 5° increments around the equilibrium geometry. The modified internal coordinates are marked in the input files with #HERE comments for transparency. Each scan point is provided as a complete .inp / .out pair. Reproducibility All calculations in this repository can be reproduced using: ORCA v5.0.3 (or newer versions with compatible input syntax) Each subdirectory represents a self-contained calculation. Running the provided input files under the specified software version will reproduce the energies, magnetic coupling constants, and electronic-structure data reported in the publication.