Charge-transfer interactions govern the trans influence and electron-induced bond activation in linear Au(i)...

Linear Au(i) complexes with the general formula of X-Au-L (X = Cl, Br, or I; L = OMe₂, SMe₂, SeMe₂, or TeMe₂) are model systems that exhibit trans influence and are directly relevant to focused electron-beam-induced deposition (FEBID), where low-energy electrons trigger precursor fragmentation. Using DFT/NBO together with ETS-NOCV/EDA and TD-DFT hole-electron analyses, we show that trends in Au-L bond strengthening and Au-X bond weakening are governed primarily by orbital-interaction/charge-transfer channels, including σ(Au-X)→σ*(Au-L) trans delocalization and ligand lone-pair donation into Au acceptor orbitals, which together modulate ΔE _orb and the Au-L Wiberg bond order. Electron-attachment thermodynamics identify the most favorable dissociation channels and define an electron-induced lability metric G _lab ≡ -ΔG _{frag, min}, where ΔG _{frag, min} is the most favorable (most negative) fragmentation free energy. The overlap metric S _r provides a trigger proxy for localized low-threshold excitations. To integrate these observables without double-counting, we construct a parsimonious precursor viability index (PVI3), combining G _lab and interaction stabilization S _int = -ΔE _int as benefits and S _r as a penalty; ΔC and WBI are retained as mechanistic correlates rather than as independent score components. The resulting ranking highlights ClAu(S/Se)Me₂ as the most balanced candidate within this series, and this work provides a reproducible framework for FEBID-style screening.