While these results are the typical sign that resonance effects are responsible for the observed control of the HOMO-LUMO energy, the degree to which resonance effect reach into the cluster core remains an open question. We consider two scenarios: a) that resonance extends from the ligand substituent all the way into the cluster core-local superatomic orbitals, or b) that resonance modulates the charge on the phosphorous binding group, which then inductively perturbs the superatomic orbitals. In the former case, we would expect to see a monotonic, or potentially linear, change in bond lengths with respect to σ p , with alternating shortened and lengthened bonds all the way to the core. In the latter case, we would expect to see a monotonic, or potentially linear, change in the charges of the phosphorous and gold Given that the charges and bond lengths are not directly observable in our experiments, we turned to quantum chemical methods to gain further insight. We focus on Au 8 (PPh 3 ) 2+ 7 because there is no uncertainty as to the isomeric structure of this cluster. To determine whether the resonance effects extend into the gold core, we analyzed the computed bond lengths and atomic charges. Resonance electron donating effects at the para-position will tend to increase the quinoidal character of the PPh 3 ligand, leading to a shortening of the C meta -C ortho and P-C bond lengths and elongation of the other two aromatic C-C bonds, as shown in the scheme on the top left of Figure . If resonance extends to the cluster core, then we expect a lengthening of the Au-P bond with decreasing σ p . On the left side of Figure is a summary of the computed bond lengths of Au 8 (PPh 3 ) 2+ 7 with each parasubstituent. We do indeed find the expected alternating pattern of shorter and longer bonds that increases in magnitude with decreasing σ p of the para substituent. Notably, the increase in the Au-P bond length is approximately the same as the increase of the C para -C meta clusters with respect to the Hammett para-parameter (σ p ). In both cases, quantities are averaged over all chemically equivalent bonds/atoms in the Au 8 (PPh 3 ) 2+ 7 system. At the top is an explanation of the color coding of the figures along with the expected trends as the para-substituent changes from H to Me to OMe, assuming resonance is the dominant effect. C i is the ipso carbon with respect to the P atom, C o is the ortho carbon, C m is the meta carbon, and C p is the para carbon. bond, indicating that the resonance effect has not decayed despite relaying through five bonds. A version of these plots with respect to σ r is given in Figure .