High resolution A-X emission data involving vibrational levels of the ground X 1Σg+ electronic state up to v″=113, spanning 99.8% of the potential well, have been acquired for three isotopomers of Rb2. While a good fit (σ̄f=1.03) to the 12 148 transition frequencies (with uncertainties ±0.001 cm−1) is obtained from an unconstrained combined-isotopomer Dunham-type analysis, it requires a large number (62) of expansion parameters, and the resulting empirical centrifugal distortion constants (CDCs) are unreliable for extrapolation to higher-J. Moreover, Dunham expansion fits using constrained theoretical values of the first six CDCs (up to Ov) fail to properly represent the data, as even higher-order CDCs are required. However, a direct fit of these data to an analytical “modified Lennard-Jones” potential energy function involving only 16 fitted parameters yields essentially the same quality of fit as did the unconstrained Dunham fit, and should be reliable for extrapolation to arbitrarily high J. This potential form incorporates the proper R−6 asymptotic behavior of the potential, and is constrained to have the theoretically predicted C6 dispersion coefficient. Although the dataset involves the three isotopomers 85,85Rb2, 85,87Rb2, and 87,87Rb2, none of the present analyses was able to determine any Born–Oppenheimer breakdown effects.
We present a detailed study of the 0 g Ϫ ( P 3/2 ) pure long-range electronic state of the 87 Rb 2 molecule. The high-resolution spectral data provided by photoassociative spectroscopy of 87 Rb 2 is analyzed by using the generalized simulated annealing method. The dipole matrix element of the 5p 87 Rb atomic state and other effective asymptotic parameters for the 0 g Ϫ ( P 3/2 ) long-range state are determined and a complete analytical description of the potential well is obtained. We extract a radiative lifetime of the 5 P 3/2 and 5 P 1/2 states equal to 26.25͑8͒ ns and 27.75͑8͒ ns, respectively, with a precision ͑0.3%͒ comparable to atomic physics experiment.
2014 Le potentiel quantique de l'état B 303A0+ou de l'iode, s'étendant depuis le niveau fondamental 03C5 = 0 jusqu'au niveau 03C5 = 80 (soit 99,96 % du puits de potentiel), a été déterminé à l'aide d'une méthode variationnelle (IPA). L'analyse de la branche externe de ce potentiel fait appel au développement multipolaire de l'énergie d'interaction limité au terme C10/R1003BD; l'énergie d'échange Vex(R) et les effets hyperfins étant négligés. Dans la région analysée (entre 7 et 12 Å), l'énergie d'échange Vex(R) estimée est faible et pourrait même être contrebalancée par la contribution du terme C12/R1203BD; de plus, l'énergie de la limite de dissociation De ainsi que les valeurs des coefficients Cn sont pratiquement insensibles au nombre de points tournants considérés. Les valeurs de De et de Cn sont trouvées respectivement égales à : De = 4 381,2492 ± 0,001 cm-1 C5 = 3,161(33) 105 cm-1 Å5 C6 = 1,506(43) 106 cm-1 Å6 C8 = 0,248(14) 108 cm-1 Å8 C1o ~ 0, 042(3) 1010cm-1 Å10 , où les incertitudes sont celles correspondant uniquement aux erreurs d'ajustement obtenues à partir des points tournants calculés par la méthode IPA.
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.