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The Journal of Chemical Physics

Electronic and rotational energy transfer in F(2P1/2)+H2 collisions at ultracold temperatures

Roman V. Krems, A. Dalgarno

Published Jul 1, 2002• 23 citations
Publisher

Abstract

The dynamics of F(2P1/2)+H2 scattering at ultracold temperatures is studied. It is shown that both the rotational and vibrational excitation of H2 molecules decrease substantially the efficiency of spin–orbit relaxation in F+H2 collisions. It is observed that the near-resonant electronic transition leading to rotational excitation of H2(j=0) is of the same magnitude at high energies as the off-resonant transition in which the rotational angular momentum of H2 is preserved but becomes dominant in ultracold collisions. The zero temperature rate constant for spin-orbit relaxation of F is computed and suggestions are made as to the chemical reactivity of F(2P1/2) atoms at ultracold temperatures. It is found that rotational relaxation of excited H2 molecules is significantly enhanced by electronic transitions in F atoms and the electronic relaxation in F(2P1/2)+H2(j>0) collisions is suppressed by rotational relaxation of H2.

DOI
10.1063/1.1480004

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The dynamics of F(2P1/2)+H2 scattering at ultracold temperatures is studied. It is shown that both the rotational and vibrational excitation of H2 molecules decrease substantially the efficiency of spin–orbit relaxation in F+H2 collisions. It is observed that the near-resonant electronic transition leading to rotational excitation of H2(j=0) is of the same magnitude at high energies as the off-resonant transition in which the rotational angular momentum of H2 is preserved but becomes dominant in ultracold collisions. The zero temperature rate constant for spin-orbit relaxation of F is computed and suggestions are made as to the chemical reactivity of F(2P1/2) atoms at ultracold temperatures. It is found that rotational relaxation of excited H2 molecules is significantly enhanced by electronic transitions in F atoms and the electronic relaxation in F(2P1/2)+H2(j>0) collisions is suppressed by rotational relaxation of H2.
We present a rigorous study of vibrational relaxation in $\text{para}\text{\ensuremath{-}}{\mathrm{H}}_{2}+\text{para}\text{\ensuremath{-}}{\mathrm{H}}_{2}$ collisions at cold and ultracold temperatures and identify an efficient mechanism of rovibrational energy transfer. If the colliding molecules are in different rotational and vibrational levels, the internal energy may be transferred between the molecules through an extremely state-selective process involving simultaneous conservation of internal energy and total rotational angular momentum. The same transition in collisions of distinguishable molecules corresponds to the rotational energy transfer from one vibrational state of the colliding molecules to another.
We report quantum dynamics calculations of F((2)P)+HCl(v,j)-->HF(v('),j('))+Cl((2)P) and F+DCl(v,j)-->DF(v('),j('))+Cl reactions at cold and ultracold temperatures. The effect of rotational and vibrational excitations of the HCl molecule on the reactivity is investigated. It is found that, in the ultracold regime, vibrational excitation of the HCl molecule from v=0 to v=2 enhances the reactivity by four orders of magnitude. The rotational excitation from j=0 to j=1 decreases the reactivity while the rotational excitation from j=0 to j=2 increases the reactivity. The overall effect of rotational excitation was found to be much smaller than vibrational excitation. The reactivity of the F+DCl system is significantly lower than that of the F+HCl case indicating the importance of quantum tunneling at low energies. For both reactions, Feshbach resonances corresponding to Fcdots, three dots, centered HCl or Fcdots, three dots, centeredDCl triatomic states occur at low energies. We also explored the validity of the coupled-states approximation for cold collisions taking the F+HCl(v=0,j=0) reaction as an illustrative example. It is found that the coupled-states approximation is generally valid for the background scattering even at low energies but it is inadequate to accurately describe the rich resonances in the energy dependence of the cross section resulting from the decay of van der Waals complexes. It is further shown that the coupled-states approximation cannot be used for scattering in the Wigner threshold regime when the molecule is initially in a rotationally excited level.
We present results of quantum mechanical scattering calculations including full rovibrational coupling on the relaxation of vibrationally excited H2{\mathrm{H}}_{2}H2​ molecules in collision with ultracold 3He{}^{3}\mathrm{He}3He and 4He{}^{4}\mathrm{He}4He atoms. The exothermic vibrational deactivation cross sections exhibit minima at translational temperatures near 10 K and show an inverse velocity dependence in accordance with Wigner's threshold law in the limit of zero kinetic energy. The corresponding rate coefficients exhibit minima before attaining constant values below ${10}^{\ensuremath{-}3}$ K. The rate coefficients increase by 3 orders of magnitude when the initial vibrational level of the molecule is raised from v=1v\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}1v=1 to v=10v\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}10v=10. The results suggest that quasibound resonance states of 3HeH2{}^{3}{\mathrm{HeH}}_{2}3HeH2​ and 4HeH2{}^{4}{\mathrm{HeH}}_{2}4HeH2​ exist, associated with each excited vibrational state of H2{\mathrm{H}}_{2}H2​, and that both the triatomic species 3HeH2{}^{3}{\mathrm{HeH}}_{2}3HeH2​ and 4HeH2{}^{4}{\mathrm{HeH}}_{2}4HeH2​ have one bound vibrational state.
II. Inelastic atom -molecule collisions 2 A. Vibrational and rotational relaxation 2 1. Collisions at cold and ultracold temperatures 2 2. Shape resonances in molecular collisions 6 3. Feshbach resonances in molecular collisions 6 B. Quasi-resonant transitions 7 C. Atom -molecular ion collisions 8 III.Chemical Reactions at ultracold temperatures 9 A. Tunneling dominated reactions 9 1.Reactions at zero temperature 10 2. Feshbach resonances in reactive scattering 12 B. Barrierless reactions 14 1.Collision systems of three alkali metal atoms 14 2. Role of PES in determining ultracold reactions 16 3.Relaxation of vibrationally excited alkali metal dimers 18 4. Reactions of heteronuclear and isotopically substituted alkali-metal dimer systems 19 IV.Inelastic molecule -molecule collisions 20 A. Molecules in the ground vibrational state 20 B. Vibrationally inelastic transitions 22 V. Summary and outlook 24 References 24 I. A. Vibrational and rotational relaxation 1. Collisions at cold and ultracold temperatures
The results from electronically non-adiabatic and adiabatic quantum reactive scattering calculations are presented for the H + HD( v = 5–9) → H + HD( v ′, j ′) reaction at ultracold collision energies from 10 nK to 60 K. Several experimentally verifiable signatures of the geometric phase are reported in the total and vibrationally and rotationally resolved rate coefficients. Most notable is the predicted 2 orders of magnitude enhancement of the rotationally resolved ultracold rates of odd symmetry relative to those of even symmetry. Prominent shape resonances appear at higher collision energies (100 mK to 20 K), which could be measured experimentally. Significant geometric phase effects are also reported on the resonance energies and lifetimes. In particular, an enhancement (suppression) of the l = 1 ( l = 2) shape resonances for HD( v = 5, 6) is predicted for even symmetry relative to those of odd symmetry.
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.