Abstract
Meteoric material injected into the atmosphere of Titan, Saturn's moon, can react with nitriles and other organic compounds that constitute Titan's atmosphere. However, specific chemical outcomes have not been fully explored. To understand the fates of meteoric metal ions in the Titan environment, reactions of Mg
and Al
with CH
CN (acetonitrile) and C
H
CN (propionitrile) were carried out using a drift cell ion reactor at room temperatures (300 K) and reduced temperatures (∼193 K) and modeled using density functional theory and coupled-cluster theory. Analysis of reactant ion electronic state distributions via electronic state chromatography revealed that Mg
was produced in our instrument exclusively in its ground (
S) state, whereas Al
was produced in both its
S ground state and
P first excited state. Mg
(
S) and Al
(
S) produce association products exclusively with both CH
CN and C
H
CN. Primary association reactions with C
H
CN occurred with higher reaction efficiencies than those with CH
CN. Mg
(
S) sequentially associates up to four nitrile ligands, and Al
(
S) associates up to three, each via the nitrile nitrogen. Computed binding energies are strongest for the first ligand and diminish with subsequent nitriles. Mg
(
S) exhibits a stronger preference for binding nitriles than Al
(
S) because its unpaired electron delocalizes to the nitrile ligands through back-bonding, whereas the lone pair on Al
(
S) remains localized on the metal center. Al
(
P) exhibited evidence of bimolecular product formation with both nitriles. Computational modeling of Al
(
P) with CH
CN suggests that the major product, AlCH
, is kinetically favored over the more energetically stable product, Al
(HCN).