A Density Functional Theory for Symmetric Radical Cations from Bonding to Dissociation

Abstract

It has been known for quite some time that approximate density functional (ADF) theories fail disastrously when describing the dissociative symmetric radical cations R(2)(+). By considering this dissociation limit, previous work has shown that Hartree-Fock (HF) theory favors the R(+1)-R(0) charge distribution, whereas DF approximations favor the R(+0.5)-R(+0.5). Yet, general quantum mechanical principles indicate that both these (as well as all intermediate) average charge distributions are asymptotically energy degenerate. Thus, HF and ADF theories mistakenly break the symmetry but in a contradicting way. In this letter, we show how to construct system-dependent long-range corrected (LC) density functionals that can successfully treat this class of molecules, avoiding the spurious symmetry breaking. Examples and comparisons to experimental data is given for R = H, He, and Ne, and it is shown that the new LC theory improves considerably the theoretical description of the R(2)(+) bond properties, the long-range form of the asymptotic potential curve, and the atomic polarizability. The broader impact of this finding is discussed as well, and it is argued that the widespread semiempirical approach which advocates treating the LC parameter as a system-independent parameter is in fact inappropriate under general circumstances.