DOI: 10.5281/zenodo.18034315
title: Supplementary Research Data for "Decomposition of magnetic coupling in μ-oxo-bridged metal complexes"

description: 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.