LAUSR

The rhombic dodecahedral nanocluster [Ag14(C≡CtBu)12Cl]+, which has been structurally characterized using X-ray crystallography, was transferred to the gas phase using electrospray ionization, where it was characterized by ion mobility (IM), vacuum ultraviolet (VUV), and ultraviolet (UV) spectroscopies in conjunction with DFT calculations. IM reveals a single peak, and modeling of the collision cross-section with the X-ray structure suggests that the cluster maintains its condensed phase structure upon transfer to the gas phase. The VUV spectra exhibit rich fragmentation, including: photoionization to give [Ag14(C≡CtBu)12Cl]2+• with an onset of 8.84 ± 0.08 eV; cluster fission fragmentation via losses of (AgC≡CtBu)n and (AgC≡CtBu)n−1(AgCl); and via reductive elimination of (tBuC≡C)2. Apart from channels associated with photoionization, similar fragment ions are observed in the UVPD spectra, although their relative intensities differ. The TDDFT absorption spectra are symmetry-allowed transitions including A...