We have employed extended multiconfiguration quasidegenerate perturbation theory, fourfold-way diabatic molecular orbitals, and configurational uniformity to develop a global three-state diabatic representation of the potential energy surfaces and their couplings for the electronically nonadiabatic reaction OH^* + H₂ → H₂O + H, where ^* denotes electronic excitation to the A ²Σ⁺ state. To achieve sign consistency of the computed diabatic couplings, we developed a graphics processing unit-accelerated algorithm called the cluster-growing algorithm. Having obtained consistent signs of the diabatic couplings, we fit the diabatic matrix elements (which consist of the diabatic potentials and the diabatic couplings) to analytic representations. Adiabatic potential energy surfaces are generated by diagonalizing the 3 × 3 diabatic potential energy matrix. The comparisons between the fitted and computed diabatic matrix elements and between the originally computed adiabatic potential energy surfaces and those generated from the fits indicate that the current fit is accurate enough for dynamical studies, and it may be used for quantal or semiclassical dynamics calculations.

A complete state-averaged active space self-consistent field (SA-CASSCF) calculation by means of the SA-CASSCF(18,14)-in-BP86 Miller–Manby embedding approach was performed to explore the ground and excited electronic states of the trans-[RuCl(NO)(NH₃)₄]²⁺ complex. Insights into the NO photodissociation mechanism and Ru–NO bonding properties are provided. In addition, spin–orbit (SO) interactions were taken into account to describe and characterize the spin-forbidden transitions observed at the low-energy regions of the trans-[RuCl(NO)(NH₃)₄]²⁺ UV-Vis spectrum. The SA-CASSCF(18,14)-in-BP86 electronic spectrum is in great agreement with the experimental data of Schreiner [Schreiner et al., Inorg. Chem., 1972, 11, 880].