The diabatic valence-hole concept

Abstract

A global diabatization scheme, based on the ``valence-hole'' concept, has been previously applied to model webs of avoided-crosssings that exist in four electronic-state symmetry manifolds of C$_2$ ($^1\Pi_g$, $^3\Pi_g$, $^1\Sigma_u^+$, $^3\Sigma_u^+$). Here, this model is extended to the electronically excited states of four more molecules: CN ($^2\Sigma^+$), N$_2$ ($^3\Pi_u$), SiC ($^3\Pi$), and Si$_2$ ($^3\Pi_g$). Many strangenesses in the spectroscopic observations (e.g., energy level structure, predissociation linewidths, and radiative lifetimes) for all four electronic state systems discussed here are accounted for by this $unified$ model. The key concept of the model is valence-hole electron configurations: $3\sigma^24\sigma1\pi^45\sigma^2$ in CN, $2\sigma_g^22\sigma_u^11\pi_{u}^43\sigma_g^21\pi_{g}^1$ in N$_2$, $5\sigma^26\sigma7\sigma^22\pi^3$ in SiC, and $4\sigma_g^24\sigma_u^15\sigma_g^22\pi_{u}^3$ in Si$_2$. These valence-hole configurations have a nominal bond order of three or higher, and correlate with high-energy separated-atom limits with an np$\leftarrow$ns (n=2,3) promotion in $one$ of the atomic constituents. This promotion results in a triply-occupied ``valence-core" (i.e., $2\sigma_g^22\sigma_u^1$ or the equivalent). On its way to dissociation, the strongly-bound diabatic valence-hole state crosses multiple weakly-bound or repulsive states, which belong to electron configurations with a completely-filled valence-core. These curve-crossings between diabatic potentials result in a network of many avoided-crossings among multiple electronic states, analogous to the well-studied electronic structure landscape of ionic-covalent crossings in strongly ionic molecules. Considering the unique role of valence-hole states in shaping the global electronic structure, the valence-hole concept should be added to our intuitive framework of chemical bonding.