Multipole-moment effects in ion–molecule reactions at low temperatures
Open access
Date
2022-02Type
- Journal Article
Abstract
We report on an experimental and theoretical investigation of the He+ + N2 reaction at collision energies in the range between 0 and kB·10 K. The reaction is studied within the orbit of a highly excited Rydberg electron after merging a beam of He Rydberg atoms (He(n), n is the principal quantum number), with a supersonic beam of ground-state N2 molecules using a surface-electrode Rydberg-Stark decelerator and deflector. The collision energy Ecoll is varied by changing the velocity of the He(n) atoms for a fixed velocity of the N2 beam and the relative yields of the ionic reaction products N+ and N2+ are monitored in a time-of-flight mass spectrometer. We observe a reduction of the total reaction-product yield of ∼30% as Ecoll is reduced from ≈kB·10 K to zero. An adiabatic capture model is used to calculate the rotational-state-dependent interaction potentials experienced by the N2 molecules in the electric field of the He+ ion and the corresponding collision-energy-dependent capture rate coefficients. The total collision-energy-dependent capture rate coefficient is then determined by summing over the contributions of the N2 rotational states populated at the 7.0 K rotational temperature of the supersonic beam. The measured and calculated rate coefficients are in good agreement, which enables us to attribute the observed reduction of the reaction rate at low collision energies to the negative quadrupole moment, Qzz, of the N2 molecules. The effect of the sign of the quadrupole moment is illustrated by calculations of the rotational-state-dependent capture rate coefficients for ion-molecule reactions involving N2 (negative Qzz value) and H2 (positive Qzz value) for |J, M〉 rotational states with J ≤ 5 (M is the quantum number associated with the projection of the rotational angular momentum vector J⃑ on the collision axis). With decreasing value of |M|, J⃑ gradually aligns perpendicularly to the collision axis, leading to increasingly repulsive (attractive) interaction potentials for diatomic molecules with positive (negative) Qzz values and to reaction rate coefficients that decrease (increase) with decreasing collision energies. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000532096Publication status
publishedExternal links
Journal / series
Physical Chemistry Chemical PhysicsVolume
Pages / Article No.
Publisher
Royal Society of ChemistryOrganisational unit
03449 - Merkt, Frédéric / Merkt, Frédéric
Funding
200478 - Precision measurements with cold molecules: Rydberg states, ions and photoionization (SNF)
743121 - Cold Ion Chemistry - Experiments within a Rydberg Orbit (EC)
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