Time-Dependent Density Functional Theory Study of Copper(II) Oxo Active Sites for Methane-to-Methanol Conversion in...

Copper-exchanged zeolites are useful materials for step-wise methane-to-methanol conversion (MMC). However, methanol yields on copper-exchanged zeolites are often modest, spurring interest in the development of active-site species that are activated at moderate temperatures, afford greater yields, and provide excellent methanol selectivities. Ultraviolet-visible (UV-vis) spectroscopy is a major tool for characterizing the active-sites and their evolution during the step-wise MMC process. However, computation of the UV-vis spectra of the copper-oxo active sites using Tamm-Dancoff time-dependent density functional theory (TDA-DFT) can be quite problematic. This has led to utilization of expensive methods based on multireference approaches, Green functions, and the Bethe-Salpeter equation. In this work, we examined the optical spectra of [CuO]⁺, [Cu₂O]²⁺, [Cu₂O₂]²⁺, and [Cu₃O₃]²⁺ species implicated in MMC in zeolites. For the larger species, we examined how agreement with experimental data is improved with increasingly larger cluster models. For [CuO]⁺, we compared TDA-DFT against restricted active space 2nd-order perturbation theory, RASPT2. We found that signature peaks for [CuO]⁺ have multireference behavior. The excited states have many configuration state functions with a double excitation character. These effects are likely responsible for the poor utility of conventional TDA-DFT methods. Indeed, we obtain good agreement with experimental data and RASPT2 after accounting for 2h/2p excitations within TDA-DFT with a previously described configuration interaction singles and doubles, CIS(D)-style scheme. This was the case for [CuO]⁺, [Cu₂O]²⁺, as well as a [Cu₂O₂]²⁺ species. Using a long-range corrected double-hybrid, ωB2PLYP, we provide for the first time computational evidence for the experimental UV-vis spectrum of the [Cu₃O₃]²⁺ active site motif.