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The Journal of Chemical Physics

Potential energy surface for spin-polarized rubidium trimer

Pavel Soldán

Published Jun 16, 2010• 25 citations
Publisher

Abstract

Potential energy surface for the lowest quartet state of the rubidium trimer is constructed, making use of the many-body decomposition. Interaction energies are calculated using the coupled-clusters method and interpolated using the reciprocal-power reproducing kernel Hilbert space interpolation method. Both the two-body and three-body nonadditive parts are extrapolated to exhibit the correct long-range behavior. Consequences for the low-energy scattering are briefly discussed.

DOI
10.1063/1.3455710

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Potential energy surface for the lowest quartet state of the rubidium trimer is constructed, making use of the many-body decomposition. Interaction energies are calculated using the coupled-clusters method and interpolated using the reciprocal-power reproducing kernel Hilbert space interpolation method. Both the two-body and three-body nonadditive parts are extrapolated to exhibit the correct long-range behavior. Consequences for the low-energy scattering are briefly discussed.
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We analyze three-body nonadditive interactions and characterize critical points on potential energy surfaces of the lowest A2B{A}_{2}BA2​B (A,B=Li,Na,K,Rb,CsA,B=\mathrm{Li},\mathrm{Na},\mathrm{K},\mathrm{Rb},\mathrm{Cs}A,B=Li,Na,K,Rb,Cs) quartet states using high-level ab initio calculations. Our calculations indicate that near equilibrium geometries, large nonadditive effects are stabilizing the systems. We also show that trimer formation reactions are always energetically allowed even for low-lying rovibrational states of heteronuclear triplet-$\ensuremath{\Sigma}$ dimers.
The three-body nonadditive interaction energy between helium atoms was calculated at 253 trimer configurations using the full-configuration-interaction (FCI) method. The analytic potential fitted to these energies is the best current representation of the three-body nonadditive interactions between helium atoms. At the equilateral triangle configuration with R=5.6 bohr, near the minimum of the total potential, the nonadditive three-body energy calculated at the FCI level amounts to -88.5 mK, compared to -98.5 mK at the coupled cluster with single, double, and noniterative triple excitations [CCSD(T)] level. The uncertainty of the former result resulting from basis set incompleteness is estimated to be 1.5 mK. The relative uncertainty of our present complete three-body fit, including the uncertainties resulting from the fitting procedure, is estimated at 2%, a fivefold improvement over the previous best potential. Overall, the FCI contribution beyond CCSD(T) is rather important, being of the same order of magnitude as the uncertainty of the sum of two-body interactions. The inclusion of this contribution makes uncertainties of the total trimer interaction energies dominated by the uncertainties of the two-body component.
We investigate the presence of Feshbach resonances in ultracold alkali-dialkali reactive collisions. A potential-energy surface of Na3{\text{Na}}_{3}Na3​ in the lowest quartet state is constructed and used in quantum scattering calculations. An analysis of scattering features is performed through a systematic variation in the nonadditive three-body interaction potential. Our results should provide useful information for interpreting future atom-molecule collision experiments.
We investigate the interaction between three rubidium atoms in highly excited (58p58p58p) Rydberg states lying along a common axis and calculate the potential energy surfaces between the three atoms. We find that three-body long-range potential wells exist in some of these surfaces, indicating the existence of very extended bound states that we label macrotrimers. We calculate the lowest vibrational eigenmodes and the resulting energy levels and show that the corresponding vibrational periods are rapid enough to be detected spectroscopically.
A potential energy surface for the lowest quartet electronic state ((4)A(')) of lithium trimer is developed and used to study spin-polarized Li+Li(2) collisions at ultralow kinetic energies. The potential energy surface allows barrierless atom exchange reactions. Elastic and inelastic cross sections are calculated for collisions involving a variety of rovibrational states of Li(2). Inelastic collisions are responsible for trap loss in molecule production experiments. Isotope effects and the sensitivity of the results to details of the potential energy surface are investigated. It is found that for vibrationally excited states, the cross sections are only quite weakly dependent on details of the potential energy surface.