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The Journal of Chemical Physics

An accurate semiempirical potential energy curve for the a3Σ+-state of KRb

Michael Schwarzer, Jan Peter Toennies

Published Sep 17, 2020• 6 citations
Publisher

Abstract

A semiempirical potential energy curve for the a3Σ+-state of the KRb molecule with only five parameters is reported. The potential is continuous over the entire range of internuclear distances and has the correct long-range attractive dispersion potential from established theory. The potential provides an equally good fit of the laser induced fluorescence Fourier transform spectroscopic data of Pashov et al. [Phys. Rev. A 76, 022511 (2007)] as their multi-parameter potential. The new potential is supported by the good agreement of the well parameters De, Re and the harmonic vibrational constant ωe with combining-rule estimates. The scattering lengths for all six isotopologues are also in excellent agreement with experiment with a 0.2% adjustment within theoretical uncertainty of the leading dispersion coefficient C6. An analysis of the harmonic vibrational constant ωe and the constant ωexe of the potential of Pashov et al. reveals a significant difference to the present potential which turned out to be due to an oscillatory deviation in their potential in the vicinity of the potential minimum. The new potential is, thus, the best available because its simplicity is ideal for further applications.

DOI
10.1063/5.0019223

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The Morse/Long Range (MLR) potential has become one of the most reliable and highly \nused potential energy functions for diatomic molecules. It includes the theoretical long range \nbehaviour that diatomic molecules are known to exhibit as they approach the dissociation \nlimit. Heavy alkali metals with adjacent electronic states often exhibit strong coupling \nbetween the spin and orbital angular momentum. The ground state X¹Σg⁺ and the lowest \nlying triplet state aᶟΣᵤ⁺ of Cs₂ exhibit such coupling effects and as a result, modeling the \nhighest vibrational states of these states is a non-trivial problem. Utilizing scattering length \nvalues obtained from published analysis of 60 Feshbach resonances, the correct form of the \npotential energy function was determined. Moreover, the scattering length values were used \nto determine the correct leading dispersion coefficient that describes the true form of the \nlong-range potential energy functions. All previous attempts to determine global potential \nenergy functions for these states have considered only the optical spectroscopic data. This is \nthe first ever effort attempting to use scattering lengths determined from cold atom collision \nexperiments in a combined analysis with conventional spectroscopic data.

•Aug 23, 2012•1 citation
A semiempirical potential energy curve for the a3Σ+-state of the KRb molecule with only five parameters is reported. The potential is continuous over the entire range of internuclear distances and has the correct long-range attractive dispersion potential from established theory. The potential provides an equally good fit of the laser induced fluorescence Fourier transform spectroscopic data of Pashov et al. [Phys. Rev. A 76, 022511 (2007)] as their multi-parameter potential. The new potential is supported by the good agreement of the well parameters De, Re and the harmonic vibrational constant ωe with combining-rule estimates. The scattering lengths for all six isotopologues are also in excellent agreement with experiment with a 0.2% adjustment within theoretical uncertainty of the leading dispersion coefficient C6. An analysis of the harmonic vibrational constant ωe and the constant ωexe of the potential of Pashov et al. reveals a significant difference to the present potential which turned out to be due to an oscillatory deviation in their potential in the vicinity of the potential minimum. The new potential is, thus, the best available because its simplicity is ideal for further applications.
-state of the heteronuclear polar molecules NaCs, KCs, and RbCs. These molecules are of current interest in experiments at ultra-cold conditions to explore the effects of the strong dipole-dipole forces on the collective many-body quantum behavior. New quantum phenomena are also anticipated in systems consisting of atomic species with different fermion/boson statistics. The model parameters are obtained by simultaneously fitting all five of the parameters to the extensive LIF-Fourier transform spectroscopy published by Tiemann and collaborators [e.g., Docenko et al. J. Phys. B: At., Mol. Opt. Phys. 39, S929-S943 (2006)], who also report best fit potential curves. Although the new potentials are in good agreement with the earlier potentials, they have the advantage that they are continuous over the entire range of internuclear distances and have the correct long-range behavior. The scattering lengths for all isotope combinations show good agreement with dedicated experiments where available. The new potentials are also in excellent agreement with combining rules based on the potentials of the homonuclear systems.
Interaction energies for the lowest triplet state a (3)Sigma(+) of KRb are calculated using high level ab initio methods. The interaction energies are then morphed so that the resulting potential energy curve yields 32 bound states and the correct scattering length for (40)K(87)Rb. Calculated vibrational spacings are shown to be in very good agreement with the available experimental Fourier transform and photoassociation vibrational data, but a different numbering scheme has to be used for the experimental vibrational assignment.
A modified semi-empirical Tang-Toennies potential model is used to describe the a3Σu+ potentials of the alkali dimers. These potentials are currently of interest in connection with the laser manipulation of the ultracold alkali gases. The fully analytical model is based on three experimental parameters, the well depth De, well location Re, and the harmonic vibrational frequency ωe of which the latter is only slightly optimized within the range of the literature values. Comparison with the latest spectroscopic data shows good agreement for Na2, K2, Rb2, and Cs2, comparable to that found with published potential models with up to 55 parameters. The differences between the reduced potential of Li2 and the conformal reduced potentials of the heavier dimers are analyzed together with why the model describes Li2 less accurately. The new model potential provides a test of the principle of corresponding states and an excellent first order approximation for further optimization to improve the fits to the spectroscopic data and describe the scattering lengths and Feshbach resonances at ultra-low temperatures.
A comprehensive study of the electronic states at the 4s+5s4s+5s4s+5s asymptote in KRb\mathrm{KRb}KRb is presented. Abundant spectroscopic data on the $a\phantom{\rule{0.2em}{0ex}}^{3}\ensuremath{\Sigma}^{+}$ state were collected by Fourier-transform spectroscopy, which allows one to determine an accurate experimental potential energy curve up to 14.8A˚14.8\phantom{\rule{0.3em}{0ex}}\mathrm{\AA{}}14.8A˚. The existing data set [C. Amiot et al., J. Chem. Phys. 112, 7068 (2000)] on the ground state $X\phantom{\rule{0.2em}{0ex}}^{1}\ensuremath{\Sigma}^{+}$ was extended by several additional levels lying close to the atomic asymptote. In a coupled channels fitting routine complete molecular potentials for both electronic states were fitted. Along with the line frequencies of the molecular transitions, recently published positions of Feshbach resonances in 40K^{40}\mathrm{K}40K and 87Rb^{87}\mathrm{Rb}87Rb mixtures [F. Ferlaino et al., Phys. Rev. A 74, 039903 (2006)] were included in the fit. This makes the derived potential curves capable for an accurate description of observed cold collision features so far. Predictions of scattering lengths and Feshbach resonances in other isotopic combinations are reported.
A new four parameter Tang-Toennies type potential model is described for the a 3Σu+ triplet state of the alkali dimers Na2, K2, Rb2, and Cs2. Compared to an earlier three parameter semi-empirical model based on the experimental well depth, De, well location, Re, and the harmonic vibrational frequency, ωe [Lau et al., J. Chem. Phys. 145, 194308 (2016)], the new model is also adjusted to be consistent with the scattering length. The results are shown to have a similar good agreement with the spectroscopic term values as the earlier model with the advantage that the scattering length is properly described. The deviations from recent potentials for Cs2 are discussed.
The Morse/Long Range (MLR) potential has become one of the most reliable and highly \nused potential energy functions for diatomic molecules. It includes the theoretical long range \nbehaviour that diatomic molecules are known to exhibit as they approach the dissociation \nlimit. Heavy alkali metals with adjacent electronic states often exhibit strong coupling \nbetween the spin and orbital angular momentum. The ground state X¹Σg⁺ and the lowest \nlying triplet state aᶟΣᵤ⁺ of Cs₂ exhibit such coupling effects and as a result, modeling the \nhighest vibrational states of these states is a non-trivial problem. Utilizing scattering length \nvalues obtained from published analysis of 60 Feshbach resonances, the correct form of the \npotential energy function was determined. Moreover, the scattering length values were used \nto determine the correct leading dispersion coefficient that describes the true form of the \nlong-range potential energy functions. All previous attempts to determine global potential \nenergy functions for these states have considered only the optical spectroscopic data. This is \nthe first ever effort attempting to use scattering lengths determined from cold atom collision \nexperiments in a combined analysis with conventional spectroscopic data.