Supplementary Research Data for "Orbital-Resolved Magnetic Exchange in Chalcogen-Bridged Fe(III) Dimers"

Overview This repository contains all computational data required to reproduce the results presented in the publication: “Orbital-Resolved Magnetic Exchange in Chalcogen-Bridged Fe(III) Dimers” 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 (μ-O), (μ-S), (μ-OH) & (μ-SH) bridged iron complexes and comprise broken-symmetry DFT (BS-DFT), CASSCF, and Difference Dedicated Configuration Interaction (DDCI) calculations, as well as geometry optimizations. All calculations were performed with ORCA v6.0.1, and the provided files are organized to allow direct reproduction of all reported results. Repository structure Each complex has a separate folder: Folder Bridging motif Active spaces Fe+III-O-Fe+III μ-O (10,10), (16,13), (20,15) Fe+III-OH-Fe+III μ-OH (10,10), (16,13), (20,15) Fe+III-S-Fe+III μ-S (10,10), (16,13), (20,15) Fe+III-SH-Fe+III μ-SH (10,10), (16,13), (20,15) Fe+III-O2-Fe+III (μ-O)₂ (10,10), (22,16) Fe+III-S2-Fe+III (μ-S)₂ (10,10), (22,16) Each complex folder contains: G-OPT/: high-spin and subsequent broken-symmetry geometry optimizations. Geometries obtained with PBE0, B3LYP, and TPSSh are compared in the manuscript; subsequent calculations use the PBE0-optimized broken-symmetry structures. BS-DFT/: single-point calculations with PBE0, TPSSh, and TPSS0, used for corresponding-orbital analysis and extraction of magnetic exchange couplings using the Yamaguchi projection. CASSCF folders for the active spaces listed above, each containing CAS+NEVPT2/ and, where feasible, DDCI-1/ and DDCI-2/ subfolders. Analyse.ods: spreadsheet documenting the orbital-resolved exchange-decoupling analysis for the complex. Computational details The DFT calculations used def2-TZVP for Fe and bridging atoms and def2-SVP for all remaining atoms, together with RIJCOSX/def2/J, D4, defGrid3, VeryTightSCF, and CPCM (acetonitrile). Geometry optimizations used VeryTightOpt; broken-symmetry solutions were generated using FlipSpin. CAS(10,10) contains the ten magnetic electrons in ten predominantly Fe 3d orbitals. Adding the bridging-chalcogen p orbitals gives CAS(16,13) for mono-μ bridges and CAS(22,16) for bis-μ bridges. CAS(20,15) additionally includes two NH₃ lone-pair orbitals in the mono-μ systems. CASSCF employed RIJK and AutoAux, followed by NEVPT2. The orbital-based analyses use singlet/triplet state-averaged CASSCF calculations. Complete CASSCF/NEVPT2 spin ladders are discussed in the manuscript. DDCI calculations used the RI-MRCI module with TSel = 10⁻⁸ and TPre = 10⁻⁴. DDCI1 and DDCI2 were performed for CAS(10,10); extended CAS(16,13) and CAS(22,16) references were treated with DDCI1. DDCI treatment of CAS(20,15) was computationally prohibitive. Exchange couplings follow Ĥ = −2J Ŝ_A · Ŝ_B, with J < 0 indicating antiferromagnetic coupling. Values in the manuscript are reported in cm⁻¹. Files and reuse The archive contains .inp input files, .out output files, and .xyz molecular coordinates. Open Analyse.ods with LibreOffice Calc or another OpenDocument-compatible application. See the archived inputs for individual calculation settings and dependencies, and the manuscript and Supporting Information for the full methodology. Cite the Zenodo dataset and associated article when reusing these data.