Structural, Thermodynamic, and Spectroscopic Evolution in the Hydration of Copper(II) Ions, Cu2+(H2O)2-8.

Gas-phase clusters of the hydrated Cu(II) cation with 2-8 water molecules were investigated using ab initio quantum chemistry. Isomer structures, energies, and vibrational spectra were computed across this size range, yielding a qualitative picture of this ion as an intact Cu2+ hydrate that also partially oxidizes the surrounding water network at equilibrium. At sufficient cluster sizes, these ion hydrates also become thermodynamically preferred over competitive Cu(II) hydroxide hydrates. Competitive coordination environments were found to exist at some cluster sizes, due to both hydrogen-bonding and d-orbital chemical effects, and the dominant coordination number was found in some cases to be temperature-dependent. Clear spectral signatures of the ion's coordination environment were computed to exist at each cluster size, which should make experimental verification of these computational predictions straightforward. Through comparison to recent studies of hydrated CuOH+, the effective charge on the metal center was shown to converge to approximately +1.5 in both cases, despite qualitatively different behavior of their radical spin densities. Therefore, nominally Cu(II) ions exhibit considerable electronic, chemical, and structural flexibility. The electronic origins of this flexibility─including key roles played by the water network itself─are investigated in this work and should provide a conceptual foundation for future studies of copper-based, water-oxidation catalysts.

Persistence of a Delocalized Radical in Larger Clusters of Hydrated Copper(II) Hydroxide, CuOH+(H2O)3-7.

The structures, vibrational spectra, and electronic properties of copper hydroxide hydrates CuOH+(H2O)3-7 were investigated with quantum chemistry computations. As a follow-up to a previous analysis of CuOH+(H2O)0-2, this investigation examined the progression as the square-planar metal coordination environment was filled and as solvation shells expanded. Four-, five-, and six-coordinate structures were found to be low-energy isomers. The delocalized radical character, which was discovered in the small clusters, was found to persist upon continued hydration, although the hydrogen-bonded water network in the larger clusters was found to play a more significant role in accommodating this spin. Partial charges indicated that the electronic structure includes more Cu2+···OH- character than was observed in smaller clusters, but this structure remains decidedly mixed with Cu+···OH· configurations and yields roughly half-oxidation of the water network in the absence of any electrochemical potential. Computed vibrational spectra for n = 3 showed congruence with spectra from recent predissociation spectroscopy experiments, provided that the role of the D2 tag was taken into account. Spectra for n = 4-7 were predicted to exhibit features that are reflective of both the mixed electronic character and proton-/hydrogen-shuttling motifs within the hydrogen-bonded water network.

Guided Ion Beam Studies of the Dy + O → DyO+ + e- Chemi-ionization Reaction Thermochemistry and Dysprosium Oxide, Carbide, Sulfide, Dioxide, and Sulfoxide Cation Bond Energies.

Guided ion beam tandem mass spectrometry (GIBMS) was used to measure the kinetic energy dependent product ion cross sections for reactions of the lanthanide metal dysprosium cation (Dy+) with O2, SO2, and CO and reactions of DyO+ with CO, O2, and Xe. DyO+ is formed through an exothermic process when Dy+ reacts with O2, whereas all other processes observed are found to be endothermic. The kinetic energy dependences of these cross sections were analyzed to yield 0 K bond dissociation energies (BDEs) for DyO+, DyC+, DyS+, DyO2+, and DySO+. The 0 K BDE for DyO+ is determined to be 5.60 ± 0.02 eV from the weighted average of six independent thresholds, which are dominated by the slightly endothermic reaction of Dy+ with SO2. Combined with the well-established Dy ionization energy (IE), this value indicates that the chemi-ionization reaction, Dy + O → DyO+ + e-, is endothermic by 0.33 ± 0.02 eV. Theoretical BDEs for Dy+-O, Dy+-C, Dy+-S, ODy+-O, and Dy+-SO were calculated at several levels of theory and basis sets for comparison with experiment with reasonable agreement achieved.

Electronic Structure and Vibrational Signatures of the Delocalized Radical in Hydrated Clusters of Copper("II") Hydroxide CuOH+(H2O)0-2.

The copper hydroxide ion, CuOH+, serves as the catalytic core in several recently developed water-splitting catalysts, and an understanding of its chemistry is critical to determining viable catalytic mechanisms. In spite of its importance, the electronic structure of this open-shell ion has remained ambiguous in the literature. In particular, computed values for both the thermodynamics of hydration and the vibrational signatures of the mono- and dihydrates have shown prohibitively large errors compared to values from recent experimental measurements. In this work, the source of this discrepancy is demonstrated to be the propensity of this ion to exist between traditional Cu(I) and Cu(II) oxidation-state limits. The spin density of the radical is accordingly shown to delocalize between the metal center and surrounding ligands, and increasing the hydration serves to exacerbate this behavior. Equation-of-motion coupled-cluster methods demonstrated the requisite accuracy to resolve the thermodynamic discrepancies. Such methods were also needed for spectral simulations, although the latter also required a direct simulation of the role of the deuterium "tag" molecules that are used in modern predissociation spectroscopy experiments. This nominally benign tag molecule underwent direct complexation with the open-valence metal ion, thereby forming a species akin to known metal-H2 complexes and strongly impacting the resulting spectrum. Thermal populations of this configuration and other more traditional noncovalently bound isomers led to a considerable broadening of the spectral lineshapes. Therefore, at least for the CuOH+(H2O)0-2 hydrates, these benchmark ions should be considered to be delocalized radical systems with some degree of multireference character at equilibrium. They also serve as a cautionary tale for the spectroscopy community, wherein the role of the D2 tag is far from benign.

Stepwise Activation of Water by Open-Shell Interactions, Cl(H2O)n=4-8,17.

Chemical activation of water by a single chlorine atom was examined computationally for clusters of chlorine radicals and water in a size regime just prior to internal hydration of water/ions, Cl·(H2O)n=4-8,17. This investigation follows a recent analysis of this radical-molecule interaction [Christensen et al. J. Phys. Chem. A 2019, 123, 8657] for n = 1-4, which demonstrated that n = 4 marked a transition in which an oxidized-water structural motif became viable, albeit high in energy. Thousands of unique isomers were computed in the present analysis, which resulted in three structural classes of isomers, including intact hydrated chlorine, hydrogen-transferred (HCl)(OH·)(H2O)n-1, and charge-transferred (Cl-)(H3O+)(OH·)(H2O)n-2 configurations. The electronic structures of these classes were investigated, along with harmonic vibrational signatures that probed the degree of water-network perturbations and generated experimentally verifiable computational predictions. The main outcome of this analysis is that the charge-transferred isomers were stabilized considerably upon increased hydration-leading to an energetic crossover with the hydrogen-transferred forms-but the degree of hydration was surprisingly still not sufficient to achieve crossover between the intact chlorine-water complexes and these charge-separated configurations. Internal hydration of the ions appears to be necessary in order to achieve this separation, which will likely occur at larger cluster sizes.

Probing the Partial Activation of Water by Open-Shell Interactions, Cl(H2O)1-4.

The partial chemical activation of water by reactive radicals was examined computationally for small clusters of chlorine and water, Cl•(H2O)n=1-4. Using an automated isomer-search procedure, dozens of unique, stable structures were computed. Among the resulting structural classes were intact, hydrated-chlorine isomers, as well as hydrogen-abstracted (HCl)(OH)(H2O)n-1 configurations. The latter showed increased stability as the degree of hydration increased, until n = 4, where a new class of structures was discovered with a chloride ion bound to an oxidized water network. The electronic structure of these three structural classes was investigated, and spectral signatures of this hydration-based evolution were connected to these electronic properties. An ancillary outcome of this detailed computational analysis, including coupled-cluster benchmarks, was the calibration of cost-effective quantum chemistry methods for future studies of these radical-water complexes.