title: Direct-potential-fit analyses yield improved empirical potentials for the ground X (1)Σ(+)(g) state of Be2.
abstract: We have performed new direct-potential-fit (DPF) analyses of the rotationally resolved A (1)Π(u)(ν'=2,3;J' =1,2)→X(1)Σ(+)(g) (ν" ∈[0,11];J" ∈[0,3]) stimulated emission pumping spectra of Be2 [J. M. Merritt, V. E. Bondybey, and M. C. Heaven, Science 324, 1548 (2009)] using two quite different analytical potential energy functions that incorporate the correct theoretically known long-range behaviour in different ways. These functions are: the damped Morse/long-range potential [R. J. Le Roy, C. C. Haugen, J. Tao, and H. Li, Mol. Phys. 109, 435 (2011)], and the Chebyshev polynomial expansion potential [L. Busevica, I. Klincare, O. Nikolayeva, M. Tamanis, R. Ferber, V. V. Meshkov, E. A. Pazyuk, and A. V. Stolyarov, J. Chem. Phys. 134, 104307 (2011)]. In contrast with the expanded Morse oscillator potential determined in the original DPF analysis of Merritt et al. [Science 324, 1548 (2009)], both of these functions unambiguously support the existence of the v″ = 11 last vibrational levels which is bound by only ∼0.5 cm(-1), and they give equivalent, essentially exact predictions for this level when using the original data set which ended at v″ = 10. These empirical potentials predict an equilibrium distance of re = 2.445(5) Å and a well depth of D(e) = 934.9(0.4) cm(-1), values which agree (within the uncertainties) with the best ab initio estimates of 2.444(10) Å and 935(10) cm(-1), respectively [J. Koput, Phys. Chem. Chem. Phys. 13, 20311 (2011)].
authors: Department of Chemistry, Lomonosov Moscow State University, Leninskie gory 1/3, 119991 Moscow, Russia.
authors: Vladimir V
authors: VV
authors: Meshkov
authors: Department of Chemistry, Lomonosov Moscow State University, Leninskie gory 1/3, 119991 Moscow, Russia.
authors: Andrey V
authors: AV
authors: Stolyarov
authors: Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
authors: Michael C
authors: MC
authors: Heaven
authors: Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
authors: Carl
authors: C
authors: Haugen
authors: Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
authors: Robert J
authors: RJ
authors: LeRoy