Double-hybrid
density functionals are currently the most accurate
density functionals for ground-state properties and electronic excitations.
Nevertheless, the lack of a long-range correction scheme makes them
unreliable when it comes to long-range excitations. For this reason,
we propose the first two time-dependent double-hybrid functionals
with correct asymptotic long-range behavior named ωB2PLYP and
ωB2GPPLYP. Herein, we demonstrate their excellent performance
and show that they are the most accurate and robust time-dependent
density functional theory methods for electronic excitation energies.
They provide a balanced description of local-valence, Rydberg, and
charge-transfer states. They are also able to tackle the difficult
first two transitions in polycyclic aromatic hydrocarbons and show
very promising results in a preliminary study on transition-metal
compounds, exemplified for titanium dioxide clusters. This work shows
that double hybrids can be systematically improved also for excitation
energies, and further work in this field is warranted.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.