Multipole-moment effects in ion–molecule reactions at low temperatures: part II – charge–quadrupole-interaction-induced suppression of the He(+) + N(2) reaction at collision energies below k(B)·10 K

We report on an experimental and theoretical investigation of the He(+) + N(2) reaction at collision energies in the range between 0 and k(B)·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 N(2) molecules using a surface-electrode Rydberg–Stark decelerator and deflector. The collision energy E(coll) is varied by changing the velocity of the He(n) atoms for a fixed velocity of the N(2) beam and the relative yields of the ionic reaction products N(+) and N(2)(+) are monitored in a time-of-flight mass spectrometer. We observe a reduction of the total reaction-product yield of ∼30% as E(coll) is reduced from ≈k(B)·10 K to zero. An adiabatic capture model is used to calculate the rotational-state-dependent interaction potentials experienced by the N(2) 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 N(2) 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, Q(zz), of the N(2) 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 N(2) (negative Q(zz) value) and H(2) (positive Q(zz) 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) Q(zz) values and to reaction rate coefficients that decrease (increase) with decreasing collision energies.