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AN ANALYTIC POTENTIAL ENERGY CURVE FOR THE $a\,^3\Sigma^+$ STATE OF KLi, DERIVED FROM OBSERVATIONS OF THE UPPER VIBRATIONAL LEVELS ONLY

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/31380

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Title: AN ANALYTIC POTENTIAL ENERGY CURVE FOR THE $a\,^3\Sigma^+$ STATE OF KLi, DERIVED FROM OBSERVATIONS OF THE UPPER VIBRATIONAL LEVELS ONLY
Creators: Salami, Houssam; Ross, A. J.; Crozet, P.; Le Roy, Robert J.; Kowalczyk, Pawel; Jastrzębski, Wlodzimierz
Issue Date: 2007
Abstract: Fourier transform resolved fluorescence spectra of the $^{39}$K$^{6}$Li molecule have been recorded in the near-infrared, following laser excitation (Coumarin 6 dye) to high vibrational levels of the $B\,^{1}\Pi$ state. The FT spectra show transitions to high vibrational levels of both the $X\,^{1}\Sigma^{+}$ and $a\,^{3}\Sigma^{+}$ electronic states. These include 147 transitions into six vibrational levels of the $a\,^{3}\Sigma^{+}$ state, which lie between 7 and 88 cm$^{-1}$ below the dissociation asymptote. Unfortunately, their energies span less than 30\% of the total ground-triplet-state well depth, and even vibrational assignment is not immediately obvious. However, fitting those data to eigenvalues of analytical model potential functions whose outer limbs incorporate the theoretically predicted long-range form, $\,V(R) \simeq D - C_6/R^6 - C_8/R^8\,$, yields complete, plausible potential curves for this state. The best fits converge to remarkably similar solutions which strongly suggest that the lowest observed level is v=5. Equilibrium parameters from these fits indicate $\, D_e =287(\pm 4) {\rm cm}^{-1}$ and $\,R_e= 4.99(\pm 0.09)$\,\AA\ for the $a\,^3\Sigma^+$ state of KLi, with $\,\omega_e= 47.3(\pm 1.5)$ and $44.2(\pm 1.5) {\rm cm}^{-1}$ for $^{39}$K$^{6}$Li and $^{39}$K$^{7}$Li, respectively. Properties of the resulting potential are compared with those of an {\em ab initio} potential and with those of the analogous states of Li$_2$, K$_2$, Na$_2$ and NaK. The optimized potential curve predicts that the last bound level of both isotopologues lies less than $\,0.002 {\rm cm}^{-1}$ below the atomic asymptote, but since these binding energies are much smaller than the current uncertainty in the ground state dissociation energy ($\pm 0.07 {\rm cm}^{-1}$), they remain subject to caution.
URI: http://hdl.handle.net/1811/31380
Other Identifiers: 2007-FE-10
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