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The recent work of the authors' group in the field of KEMS studies of intermetallic gaseous molecules is
reviewed. Examples are given of systems such as intragroup 14 diatomic molecules, -tri- and tetratomic species in the Si-
Sn systems, and diatomic species containing Group 11 elements. Special attention is given to species containing heavy
metals, where relativistic effects can play an important role in the stabilization or destabilization of the chemical bond.
The results of the ab initio investigation of the same species at various levels of theory, up to CCSD(T), are also reported,
showing the importance of combining the experimental and theoretical study of intermetallic molecules.