Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 109, Issue 48, Pages 11006-11014Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp0534479
Keywords
-
Ask authors/readers for more resources
Binding or potential energy curves have been calculated for the ground-state diatomics H-2(+), He-2(+), LiH+, H-2, N-2, and C-2, for the transition state H-3, and for the triplet first excited state of H-2 using the nonempirical density functionals from the first three rungs of a ladder of approximations: the local spin density (LSD) approximation, the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the Tao-Perdew-Staroverov-Scuseria (TPSS) meta GGA. Good binding energy curves in agreement with coupled cluster or configuration interaction calculations are found from the PBE GGA and especially from the TPSS meta GGA. Expected exceptions are the symmetric radicals H-2(+) and He-2(+), where the functionals suffer from self-interaction error, and the exotically bonded C-2. Although the energy barrier for the reaction H-2(+) H -> H + H-2 is better in PBE than in TPSS, the transition state H-3 is a more properly positioned and curved saddle point of the energy surface in TPSS. The triplet first excited state of H-2 obeys the Aufbau principle and thus is one of the exceptional excited states that are computable in principle from the ground-state functional. The PBE GGA and TPSS meta GGA are useful not only for chemical applications but also for the construction of higher-rung nonempirical functionals that can further improve the binding energy curves.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available