The difference in the variation of E hyb with ϵ d at large, negative ϵ d (< -3.5 eV for 4d and 5d metals and < -1.9 eV for 3d metals) gives rise to scatter in linear scaling relations between O* and C* along a fixed row of transition metals. For O*, the variation of E chem in this large, negative ϵ d region is determined solely by E ortho as E hyb → 0. For C*, all regions of ϵ d are jointly determined by the contributions of E hyb and E ortho . This mismatch of energy contributions, E ortho alone for O* and E hyb + E ortho for C*, explains why metals such as Cu, Ag and Au in the large, negative ϵ d region fall off linear scaling relationships.