Ab initio long-range interaction and adiabatic channel capture model for ultracold reactions between the KRb molecules

A A Buchachenko; A V Stolyarov; M M Szczȩśniak; G Chałasiński

doi:10.1063/1.4752740

Ab initio long-range interaction and adiabatic channel capture model for ultracold reactions between the KRb molecules

J Chem Phys. 2012 Sep 21;137(11):114305. doi: 10.1063/1.4752740.

Authors

A A Buchachenko¹, A V Stolyarov, M M Szczȩśniak, G Chałasiński

Affiliation

¹ Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow 119991, Russia.

PMID: 22998260
DOI: 10.1063/1.4752740

Abstract

The coefficients at the lowest-order electrostatic, induction, and dispersion terms of the anisotropic long-range potential between the two KRb((1)Σ(+)) molecules are evaluated through the static and dynamic molecular properties using the ab initio coupled cluster techniques. Adiabatic channel potentials for the ground-state molecules are obtained and used for the numerical quantum capture probability calculations in the spirit of the statistical adiabatic channel models. Capture rate coefficients for indistinguishable (polarized) and distinguishable (unpolarized) molecules at temperatures below 10 μK agree well with those computed with the simple isotropic dispersion R(-6) potential, but underestimate the measured ones [Ospelkaus et al., Science 327, 853 (2010)] up to a factor of 3. Preliminary assessment of the effects of higher-order long-range terms, retardation of dispersion forces, and magnetic dipole-dipole interaction does not offer any clear perspectives for drastic improvement of the capture approximation for the reactions studied.