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arXiv:1312.4796 · The Journal of Chemical Physics

Theoretical study of the buffer-gas cooling and trapping of CrH(X6Σ+) by 3He atoms

Jacek A. Kłos, Michał Hapka, Grzegorz Chałasiński, Philippe Halvick, Thierry Stoecklin

Published Dec 2, 2016• 5 citations
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Abstract

We present a theoretical study of the Zeeman relaxation of the magnetically trappable lowest field seeking state of CrH(X6Σ+) in collisions with 3He. A two dimensional potential energy surface (PES) was calculated with the partially spin-restricted coupled cluster singles, doubles, and non-iterative triples [RCCSD(T)] method. The global minimum was found for the collinear He⋯Cr–H geometry with the well depth of 1143.84 cm−1 at Re = 4.15 a0. Since the RCCSD(T) calculations revealed a multireference character in the region of the global minimum, we performed additional calculations with the internally contracted multireference configuration interaction with the Davidson correction (ic-MRCISD+Q) method. The resulting PES is similar to the RCCSD(T) PES except for the region of the global minimum, where the well depth is 3032 cm−1 at Re = 3.8 a0. An insight into the character of the complex was gained by means of symmetry-adapted perturbation theory based on unrestricted Kohn-Sham description of the monomers. Close coupling calculations of the Zeeman relaxation show that although the ΔMJ=MJ′−MJ = −1 and −2 transitions are the dominant contributions to the collisional Zeeman relaxation, ΔMJ<−2 transitions cannot be neglected due to the large value of CrH spin-spin constant. The calculated elastic to inelastic cross section ratio is 1600 for the RCCSD(T) PES and 500 for the MRCISD+Q PES, while the estimate from the buffer-gas cooling and magnetic trapping experiment is 9000.

DOI
10.1063/1.4968529

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We present a theoretical study of the Zeeman relaxation of the magnetically trappable lowest field seeking state of CrH(X6Σ+) in collisions with 3He. A two dimensional potential energy surface (PES) was calculated with the partially spin-restricted coupled cluster singles, doubles, and non-iterative triples [RCCSD(T)] method. The global minimum was found for the collinear He⋯Cr–H geometry with the well depth of 1143.84 cm−1 at Re = 4.15 a0. Since the RCCSD(T) calculations revealed a multireference character in the region of the global minimum, we performed additional calculations with the internally contracted multireference configuration interaction with the Davidson correction (ic-MRCISD+Q) method. The resulting PES is similar to the RCCSD(T) PES except for the region of the global minimum, where the well depth is 3032 cm−1 at Re = 3.8 a0. An insight into the character of the complex was gained by means of symmetry-adapted perturbation theory based on unrestricted Kohn-Sham description of the monomers. Close coupling calculations of the Zeeman relaxation show that although the ΔMJ=MJ′−MJ = −1 and −2 transitions are the dominant contributions to the collisional Zeeman relaxation, ΔMJ<−2 transitions cannot be neglected due to the large value of CrH spin-spin constant. The calculated elastic to inelastic cross section ratio is 1600 for the RCCSD(T) PES and 500 for the MRCISD+Q PES, while the estimate from the buffer-gas cooling and magnetic trapping experiment is 9000.
We present a theoretical study of the Zeeman relaxation of the magnetically trappable lowest field seeking state of MnH (${}^{7}\ensuremath{\Sigma}$) in collisions with 3He^{3}\mathrm{He}3He. We analyze the collisional Zeeman transition mechanism as a function of the final diatomic state and its variation as a function of an applied magnetic field. We show that as a result of this mechanism the levels with $\ensuremath{\Delta}{M}_{j}>2$ give negligible contributions to the Zeemam relaxation cross section. We also compare our results to the experimental cross sections obtained from the buffer-gas cooling and magnetic trapping of this molecule and investigate the dependence of the Zeeman relaxation cross section on the accuracy of the three-body interaction at ultralow energies.
A theoretical investigation of the He-PH (${}^{3}{\ensuremath{\Sigma}}^{\ensuremath{-}}$) complex is presented. We perform ab initio calculations of the interaction potential energy surface and discuss its error bounds with relevance to cold collisions, and we carry out accurate calculations of bound energy levels of the complex including the molecular fine structure and magnetic-field effect. We find the potential has two shallow minima and supports ten and 13 bound levels in complex with 3{}^{3}3He and 4{}^{4}4He, respectively. Based on the potential the quantum scattering calculations are then implemented for elastic and inelastic cross sections of the magnetically trappable low-field-seeking state of PH (${}^{3}{\ensuremath{\Sigma}}^{\ensuremath{-}}$) in collision with 3{}^{3}3He atom. The cold-collision properties and the influence of the external magnetic field as well as the effect of the uncertainty of interaction potential on the collisionally induced Zeeman relaxation are explored and discussed in detail. The ratio of elastic to inelastic cross sections is large over a wide range of collision energy, magnetic field, and scaling factor of the potential, so that helium buffer-gas loading and evaporative cooling of PH is a good prospect.
Ab initio calculations of cross sections and rate constants for elastic scattering and Zeeman relaxation in collisions of $\mathrm{NH}(X{}^{3}{\ensuremath{\Sigma}}^{\ensuremath{-}})$ molecules with 3He{}^{3}\mathrm{He}3He atoms in a magnetic field are presented and the mechanism for Zeeman transitions in ground-state ${}^{3}\ensuremath{\Sigma}$ molecules is established. The potential surface for He-NH interaction is obtained using all-electron coupled-cluster calculations with single, double, and noniterative triple excitations in a basis set augmented by bond functions. The ratio of the rates for elastic energy transfer and Zeeman relaxation in NH-3He{}^{3}\mathrm{He}3He collisions exceeds 105{10}^{5}105 at temperatures between 0.50.50.5 and 1 K.
Cold collisions of polyatomic molecular radicals with S-state atoms in a magnetic field: An ab initio study of He + CH2(X~){\rm CH}_2(\tilde{X})CH2​(X~) CH 2(X) 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.
We report on the buffer-gas cooling and trapping of CrH and MnH molecules in a magnetic quadrupole trap with densities on the order of ${10}^{6}\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}3}$ at a temperature of 650mK650\phantom{\rule{0.3em}{0ex}}\mathrm{mK}650mK. Storage times of up to 180ms180\phantom{\rule{0.3em}{0ex}}\mathrm{ms}180ms have been observed, corresponding to a 20-fold lifetime enhancement with respect to the field-free diffusion through the 3He^{3}\mathrm{He}3He buffer-gas. Using Monte Carlo trajectory simulations, inelastic molecule-3He^{3}\mathrm{He}3He collision cross sections of $1.6\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}18}$ and $3.1\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}17}\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{2}$ are extracted for CrH and MnH, respectively. Furthermore, elastic molecule-3He^{3}\mathrm{He}3He collision cross sections of $1.4(\ifmmode\pm\else\textpm\fi{}0.5)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}14}\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{2}$ are determined for both species. We conclude that the confinement time of these molecules in a magnetic trapping field is limited by inelastic collisions with the helium atoms leading to Zeeman relaxation.
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