Iodization Threshold in Size-Dependent Reactions of Lead Clusters Pbn+ with Iodomethane

• Utilizing a magnetron-sputtering (MagS) source in tandem with a multiple-ion laminar flow tube (MIFT) reactor and a customized triple quadrupole mass spectrometer (TQMS), we have prepared clean Pbn+ (n = 1−13) clusters and measured their reactivity with iodomethane under high carrier gas pressures. Strong size dependences are found for the reactivity of these cationic Pbn+ clusters with CH3I. For the Pbn+ with n ≤ 4, iodinated clusters PbnI+ were found to be the dominant products, in strong contrast to n > 4 where no such products were seen. Quantum chemical studies show that with an increasing number of Pb atoms, the Pb−Pb interatomic interactions become stronger compared with the Pb−I bonding in PbnI+ clusters. Furthermore, the reactions of Pb1−4+ with CH3I have fairly small transition state energy barriers, in contrast to those for Pbn>4 + clusters which have magnitudes that will prevent reactions under the ambient conditions.

Ämnesord

NATURVETENSKAP  -- Kemi -- Fysikalisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Physical Chemistry (hsv//eng)

Nyckelord

Lead clusters

reactivity

Publikations- och innehållstyp

ref (ämneskategori)

art (ämneskategori)