Valence Bond Alternative Yielding Compact And Accurate Wave Functions For Challenging Excited States. Application To Ozone And Sulfur Dioxide

A novel state-averaged version of ab initio nonorthogonal valence bond method is described, for the sake of accurate theoretical studies of excited states in the valence bond framework. With respect to standard calculations in the molecular orbital framework, the state-averaged breathing-orbital valence bond (BOVB) method has the advantage to be free from the penalizing constraint for the ground and excited state(s) to share the same unique set of orbitals. The ability of the BOVB method to faithfully describe excited states and to compute accurate transition energies from the ground state is tested on the five lowest-lying singlet electronic states of ozone and sulfur dioxide, among which 1(1)B(2) and 2(1)A(1) are the challenging ones. As the 1(1)A(2), 1(1)B(1), and 1(1)B(2) states are of different symmetries than the ground state, they can be calculated at the state-specific BOVB level. On the other hand, the 2(1)A(1) states and the 1(1)A(1) ground states, which are of like symmetry, are calculated with the state-averaged BOVB technique. In all cases, the calculated vertical energies are close to the experimental values when available, and at par with the most sophisticated calculations in the molecular framework, despite the extreme compactness of the BOVB wave functions, made of no more than 5-9 valence bond structures in all cases. The features that allow the combination of compactness and accuracy in challenging cases are analyzed. For the "ionic" 1(1)B(2) states, which are the site of important charge fluctuations, it is because of the built-in dynamic correlation inherent to the BOVB method. For the 2(1)A(1) ones, this is the fact that these states have the degree of freedom of having different orbitals than the ground states, even though they are of like symmetry and calculated simultaneously using the newly implemented state-average BOVB algorithm. Finally, the description of the excited states in terms of Lewis structures is insightful, rationalizing the fast ring closure for the 2(1)A(1) state of ozone and predicting some diradical character in the so-called "ionic" 1(1)B(2) states.