Cold collisions of heavy (2)Sigma molecules with alkali-metal atoms in a magnetic field: Ab initio analysis and prospects for sympathetic cooling of SrOH((2)Sigma(+)) by Li(S-2)

Abstract

We use accurate ab initio and quantum scattering calculations to explore the prospects for sympathetic cooling of the heavy molecular radical SrOH((2)Sigma(+)) by ultracold Li atoms in a magnetic trap. Our ab initio calculations show that the chemical reaction between spin-polarized Li and SrOH, which occurs on the triplet Li-SrOH potential energy surface (PES), is strongly endothermic and hence energetically forbidden at ultralow temperatures. The chemical reaction Li(S-2) + SrOH((2)Sigma(+)) -> Sr(S-1) + LiOH((1)Sigma(+)) occurs barrierlessly on the singlet PES and is exothermic by 2505 cm(-1). A two-dimensional PES for the triplet electronic state of Li-SrOH is calculated ab initio using the partially spin-restricted coupled clustermethod with single, double, and perturbative triple excitations and a large correlation-consistent basis set. The highly anisotropic PES has a deep global minimum in the skewed Li-HOSr geometry with D-e = 4932 cm(-1) and saddle points in collinear configurations. Our quantum scattering calculations predict low spin-relaxation rates in fully spin-polarized Li + SrOH collisions with the ratios of elastic to inelastic collision rates well in excess of 100 over a wide range of magnetic fields (1-1000 G) and collision energies (10(-5) to 0.1 K), suggesting favorable prospects for sympathetic cooling of SrOH molecules with spin-polarized Li atoms in a magnetic trap. We find that spin relaxation in Li + SrOH collisions occurs via a direct mechanism mediated by the magnetic dipole-dipole interaction between the electron spins of Li and SrOH, and that the indirect (spin-rotation) mechanism is strongly suppressed. The upper limit to the Li + SrOH reaction rate coefficient calculated for the singlet PES using adiabatic capture theory is found to decrease from 4x10(-10) cm(3)/s to a limiting value of 3.5x10(-10) cm(3)/s with decreasing temperature from 0.1 K to 1 mu K