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The Journal of Chemical Physics

Fine-structure effects in vibrational relaxation at ultralow temperatures

Alessandro Volpi, John L. Bohn

Published Jun 30, 2003• 12 citations
Publisher

Abstract

We have calculated cross sections for vibrational quenching in collisions of O217(X 3∑g−) with He3 at cold and ultracold temperatures, explicitly accounting for the electronic spin degree of freedom. The observed population of the final spin-rotational levels can be interpreted on the basis of useful “propensity rules” governing the intensity of the collision-induced transitions. In addition, it is found that the orientation of the molecular spin is reasonably robust against collisional relaxation, even in vibrationally excited states. This finding implies that magnetic trapping of vibrationally excited, but rotationally and translationally cold, molecules may be possible.

DOI
10.1063/1.1577113

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We have calculated cross sections for vibrational quenching in collisions of O217(X 3∑g−) with He3 at cold and ultracold temperatures, explicitly accounting for the electronic spin degree of freedom. The observed population of the final spin-rotational levels can be interpreted on the basis of useful “propensity rules” governing the intensity of the collision-induced transitions. In addition, it is found that the orientation of the molecular spin is reasonably robust against collisional relaxation, even in vibrationally excited states. This finding implies that magnetic trapping of vibrationally excited, but rotationally and translationally cold, molecules may be possible.
We present cross sections for rotational, vibrational, and fine-structure transitions in He–CaH(2Σ) collisions at cold and ultracold temperatures calculated using the ab initio potential energy surface reported in the preceding paper. Rotational quenching is fast, vibrational quenching is slow. The spin-rotational interaction, although small and having no influence at temperatures above 10 K, changes significantly the rate coefficients for rotational quenching at lower temperatures. The theoretical rotational, vibrational, and elastic cross sections are compared with the results of a buffer gas cooling experiment carried out at a temperature of about 0.4 K. The theoretical predictions for the vibrational and elastic cross sections are larger than the measured values. The sensitivity to the potential energy surface is explored. A modified surface diminishes but does not remove the differences between theory and experiment.
In a recent work we compared spin-free collisions of N2+\mathrm{N}_{2}{}^{+}N2​+ with 3He^{3}\mathrm{He}3He and 4He^{4}\mathrm{He}4He using a newly developed potential energy surface. We found that such collisions exhibit a strong isotope effect in the ultracold regime. In the present study we consider the role of the spin-rotation interaction in cold $\mathrm{He}\text{\ensuremath{-}}\mathrm{N}_{2}{}^{+}$ collisions. We find that our spin-free vibrational quenching cross sections are not affected. Conversely, the cross sections for rotational quenching are strongly modified in the ultracold regime and exhibit resonance structures which are analyzed. These structures, which are not observed when the spin-rotation interaction is omitted, are shown to be due to the Feshbach resonances associated with the nonconservation of parity.
We explore the quantum dynamics of nuclear spin relaxation in cold collisions of 1 Σ + molecules with structureless atoms in an external magnetic field. To this end, we develop a rigorous coupled-channel methodology, which accounts for rotational and nuclear spin degrees of freedom of 1 Σ + molecules and their interaction with an external magnetic field as well as anisotropic atom–molecule interactions. We apply the methodology to study the collisional relaxation of the nuclear spin sublevels of 13 CO molecules immersed in a cold buffer gas of 4 He atoms. We find that nuclear spin relaxation in the ground rotational manifold ( N = 0) of 13 CO occurs extremely slowly due to the absence of direct couplings between the nuclear spin sublevels. The rates of collisional transitions between the rotationally excited ( N = 1) nuclear spin states of 13 CO are generally much higher due to the direct nuclear spin–rotation coupling between the states. These transitions obey selection rules, which depend on the values of space-fixed projections of rotational and nuclear spin angular momenta ( M N and M I ) for the initial and final molecular states. For some initial states, we also observe a strong magnetic field dependence, which can be understood by using the first Born approximation. We use our calculated nuclear spin relaxation rates to investigate the thermalization of a single nuclear spin state of 13 CO( N = 0) immersed in a cold buffer gas of 4 He. The calculated nuclear spin relaxation times ( T 1 ≃ 1 s at T = 1 K at a He density of 10 –14 cm –3 ) display a steep temperature dependence decreasing rapidly at elevated temperatures due to the increased population of rotationally excited states, which undergo nuclear spin relaxation at a much faster rate. Thus, long relaxation times of N = 0 nuclear spin states in cold collisions with buffer gas atoms can be maintained only at sufficiently low temperatures ( k B T ≪ 2 B e ), where B e is the rotational constant.
The study of molecular inelastic collision processes at cold and ultracold temperatures is of considerable interest as schemes are currently being developed to efficiently cool and trap neutral polar molecules. In this work, quantum-mechanical scattering calculations are presented for the quenching of rotationally excited CO due to collisions with H, He and H 2 for collision energies between 10 −5 and 10 cm −1 . The calculations were performed using the close-coupling approach and the coupled-states approximation. Cross sections for the quenching of the j = 1–10, 20, 30 and 40 levels of CO are presented and mechanism and trends of energy transfer in these systems are discussed.
Quantum mechanical methods are employed to obtain superelastic cross sections involving H 2 and N 2 molecules, in excited rotational states, colliding with electrons at the very low collision energies which are encountered in cold trap experiments. This computational analysis intends to explore the feasibility of cold electrons for the collisional quenching of molecular gases down to the nanokelvin regimes. The results are obtained using rigorous coupled-channel (CC) calculations in the laboratory frame of reference which allows one to correctly describe the cross section behaviour at ultralow energies. The results are analysed down to the ultracold region of validity of Wigner's law, where it is found that electron-driven collisions exhibit substantial efficiency for the quenching of rotational populations in molecular gases involving the title systems.
Cold collisions involving highly rotationally excited diatomic molecules are investigated. As the translational energy is lowered, the total inelastic cross section decreases sharply for specific channels where quasiresonant transitions are no longer energetically allowed. Rate coefficients are given for collisional quenching of rotationally excited H2,D2,T2,{\mathrm{H}}_{2},{\mathrm{D}}_{2},{\mathrm{T}}_{2},H2​,D2​,T2​, and O2{\mathrm{O}}_{2}O2​ at zero temperature. The specific rotational states that are stable against collisional relaxation would be interesting prospects for cooling and trapping. The application of collisional cooling methods together with recently developed schemes for producing rotationally hot molecules may allow high densities of ultracold ``super rotors'' to be achieved.