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arXiv:cond-mat/0211065 · Physical Review A

Three-body nonadditive forces between spin-polarized alkali-metal atoms

Pavel Soldán, Marko T. Cvitaš, Jeremy M. Hutson

Published May 28, 2003• 93 citations
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Abstract

Three-body nonadditive forces in systems of three spin-polarized alkali-metal atoms (Li, Na, K, Rb, and Cs) are investigated using high-level ab initio calculations. The nonadditive forces are found to be large, especially near the equilateral equilibrium geometries. For Li, they increase the three-atom potential well depth by a factor of 4 and reduce the equilibrium interatomic distance by $1.07\mathrm{\AA{}}.$ The nonadditive forces originate principally from chemical bonding arising from $\mathrm{sp}$ mixing effects.

DOI
10.1103/physreva.67.054702

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Three-body nonadditive forces in systems of three spin-polarized alkali-metal atoms (Li, Na, K, Rb, and Cs) are investigated using high-level ab initio calculations. The nonadditive forces are found to be large, especially near the equilateral equilibrium geometries. For Li, they increase the three-atom potential well depth by a factor of 4 and reduce the equilibrium interatomic distance by 1.07A˚.1.07\mathrm{\AA{}}.1.07A˚. The nonadditive forces originate principally from chemical bonding arising from sp\mathrm{sp}sp mixing effects.
We theoretically characterize interactions, energetics, and chemical reaction paths in ionic two-body and three-body systems of alkali-metal and alkaline-earth-metal atoms in the context of modern experiments with cold hybrid ion-atom mixtures. Using ab initio techniques of quantum chemistry such as the coupled-cluster method, we calculate ground-state electronic properties of all diatomic AB+A{B}^{+}AB+ and most of the triatomic A2B+{A}_{2}{B}^{+}A2​B+ molecular ions consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and Yb atoms. Different geometries and wave-function symmetries of the ground state are found for different classes of molecular ions. We analyze intermolecular interactions in the investigated systems including additive two-body and nonadditive three-body ones. As an example we provide two-dimensional interaction potential-energy surfaces for KRb++K{\mathrm{KRb}}^{+}+\mathrm{K}KRb++K and Rb++Sr2{\mathrm{Rb}}^{+}+{\mathrm{Sr}}_{2}Rb++Sr2​ mixtures. We identify possible channels of chemical reactions based on the energetics of the reactants. The present results may be useful for investigating controlled chemical reactions and other applications of molecular ions formed in cold hybrid ion-atom systems.
The van der Waals coefficients, C6,C8,{C}_{6},{C}_{8},C6​,C8​, and C10{C}_{10}C10​ for the alkali-metal (Li, Na, K, and Rb) and alkaline-earth-metal (Be, Mg, Ca, and Sr) atoms are estimated by a combination of ab initio and semiempirical methods. Polarizabilities and atom-wall coefficients are given as a diagnostic check, and the lowest order nonadiabatic dispersion coefficient, D8{D}_{8}D8​ and the three-body coefficient, C9{C}_{9}C9​ are also presented. The dispersion coefficients are in agreement with the available relativistic many-body perturbation theory calculations. The contribution from the core was included by using constrained sum rules involving the core polarizability and Hartree-Fock expectation values to estimate the f-value distribution.
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.
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Collisions of atoms and molecules in external electromagnetic fields can depolarize electronic and nuclear spins, leading to decoherence of quantum superposition states. The fundamental microscopic processes giving rise to spin depolarization are spin exchange and spin relaxation. In this work, we present an analysis of spin exchange transitions in collision of alkali metal atoms with 3He. We use accurate ab initio calculations to evaluate the electron spin density of Li-He and the interaction energy of Rb-He. The Fermi contact interaction constants for the complexes of Na, K, and Rb atoms with 3He are extracted from the measured frequency shift enhancement factors using the ab initio interaction potentials. The spin density calculations also yield the hyperfine pressure shift of Li-He.
We study the nonadditive part of the long-range interaction among three alkali-metal atoms in their ground states. Using nondegenerate perturbation theory, up to the third order, we have computed the dispersion coefficients C for three alkali-metal atoms interacting via their electric dipole moments. Both heteronuclear and homonuclear cases are considered. The numerical values for the C coefficients suggest that such three-body dipole interaction effects may not be neglected in the description of the long-range surface potential interaction for alkali-metal atoms. Furthermore, we show that approximate formulas for C of Midzuno and Kihara [J. Phys. Soc. Jpn. 11, 1045 (1956)] give results in excellent agreement with results of our calculations. Comparisons are given of our results with results of others and with results of other approximate formulas. The effect on our results for the C coefficient of uncertainties in the experimental values of the static dipole polarizabilities, on which our results depend, is also analyzed.