Revisiting the geometry of nd10 (n+1)s0 [M(H2O)]p+ complexes using four‐component relativistic DFT calculations and scalar relativistic correlated CSOV energy decompositions (Mp+ = Cu+, Zn2+, Ag+, Cd2+, Au+, Hg2+)

Hartree–Fock and DFT (B3LYP) nonrelativistic (scalar relativistic pseudopotentials for the metallic cation) and relativistic (molecular four‐component approach coupled to an all‐electron basis set) calculations are performed on a series of six nd10 (n+1)s0 [M(H2O)]p+ complexes to investigate their geometry, either planar C2v or nonplanar Cs. These complexes are, formally, entities originating from the complexation of a water molecule to a metallic cation: in the present study, no internal reorganization has been found, which ensures that the complexes can be regarded as a water molecule interacting with a metallic cation. For [Au(H2O)]+ and [Hg(H2O)]2+, it is observed that both electronic correlation and relativistic effects are required to recover the Cs structures predicted by the four‐component relativistic all‐electron DFT calculations. However, including the zero‐point energy corrections makes these shallow Cs minima vanish and the systems become floppy. In all other systems, namely [Cu(H2O)]+, [Zn(H2O)]2+, [Ag(H2O)]+, and [Cd(H2O)]2+, all calculations predict a C2v geometry arising from especially flat potential energy surfaces related to the out‐of‐plane wagging vibration mode. In all cases, our computations point to the quasi‐perfect transferability of the atomic pseudopotentials considered toward the molecular species investigated. A rationalization of the shape of the wagging potential energy surfaces (i.e., single well vs. double well) is proposed based on the Constrained Space Orbital Variation decompositions of the complexation energies. Any way of stabilizing the lowest unoccupied orbital of the metallic cation is expected to favor charge‐transfer (from the highest occupied orbital(s) of the water ligand), covalence, and, consequently, Cs structures. The CSOV complexation energy decompositions unambiguously reveal that such stabilizations are achieved by means of relativistic effects for [Au(H2O)]+, and, to a lesser extent, for [Hg(H2O)]2+. Such analyses allow to numerically quantify the rule of thumb known for Au+ which, once again, appears as a better archetype of a relativistic cation than Hg2+. This observation is reinforced due to the especially high contribution of the nonadditive correlation/relativity terms to the total complexation energy of [Au(H2O)]+. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 142–156, 2006

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