Alexander Dalgarno

Cold collisions of polyatomic molecular radicals with S-state atoms in a magnetic field: An ab initio study of He + CH 2(X̃) collisions

We develop a rigorous quantum mechanical theory for collisions of polyatomic molecular radicals with S-state atoms in the presence of an external magnetic field. The theory is based on a fully uncoupled space-fixed basis set representation of the multichannel scattering wave function. Explicit expressions are presented for the matrix elements of the scattering Hamiltonian for spin-1/2 and spin-1 polyatomic molecular radicals interacting with structureless targets. The theory is applied to calculate the cross sections and thermal rate constants for spin relaxation in low-temperature collisions of the prototypical organic molecule methylene [CH(2)(X(3)B(1))] with He atoms. To this end, two accurate three-dimensional potential energy surfaces (PESs) of the He-CH(2)(X(3)B(1)) complex are developed using the state-of-the-art coupled-cluster method including single and double excitations along with a perturbative correction for triple excitations and large basis sets. Both PESs exhibit shallow minima and are weakly anisotropic. Our calculations show that spin relaxation in collisions of CH(2), CHD, and CD(2) molecules with He atoms occurs at a much slower rate than elastic scattering over a large range of temperatures (1 μK-1 K) and magnetic fields (0.01-1 T), suggesting excellent prospects for cryogenic helium buffer-gas cooling of ground-state ortho-CH(2)(X(3)B(1)) molecules in a magnetic trap. Furthermore, we find that ortho-CH(2) undergoes collision-induced spin relaxation much more slowly than para-CH(2), which indicates that magnetic trapping can be used to separate nuclear spin isomers of open-shell polyatomic molecules.

Anisotropic Hyperfine Interactions Limit the Efficiency of Spin-Exchange Optical Pumping of 3He Nuclei

We establish the existence of a fundamental limit to the efficiency of spin-exchange optical pumping of He nuclei by collisions with spin-polarized alkali-metal atoms. Using accurate ab initio calculations of molecular interactions and scattering properties, we show that the maximum He spin polarization that can be achieved in spin-exchange collisions with potassium (K) and silver (Ag) atoms is limited by the anisotropic hyperfine interaction. We find that spin exchange in Ag-He collisions occurs much faster than in K-He collisions, suggesting the possibility of using Ag in spin-exchange optical pumping experiments to increase the production rate of hyperpolarized He. Our analysis indicates that measurements of trap loss rates of S atoms in the presence of cold He gas may be used to probe anisotropic spin-exchange interactions in atom-He collisions.