Abstract

A new set of rovibronic terms in the range between ∼37000 and 39000cm-1 is reported for the copper dimer isotopologues 63Cu2 and 63Cu65Cu. These terms were measured by two-color four-wave mixing spectroscopy yielding rotationally resolved vibronic bands at a resolution ∼0.04cm-1. The complex spectral structure is analyzed and a tentative assignment of a new electronic state of gerade symmetry named {36.9}0g+ is proposed. The assignment is corroborated by ab initio calculations carried out at the multi-reference configuration interaction level of theory.

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