Cc. Arnold et Dm. Neumark, STUDY OF SI4 AND SI4- USING THRESHOLD PHOTODETACHMENT (ZEKE) SPECTROSCOPY, The Journal of chemical physics, 99(5), 1993, pp. 3353-3362
The threshold photodetachment (ZEKE) spectrum of Si4- is presented. Al
though no transitions to the ground state of Si4 are observed, we obta
in detailed information on the anion and several of the low-lying exci
ted states of neutral Si4. The spectrum shows a long progression of we
ll-resolved transitions between the D2h B-2(2g) rhombus anion and v2 v
ibrational levels of the first excited D2h B-3(3u) neutral. The length
and spacing of the progression is consistent with ab initio calculati
ons performed by Rohlfing and Raghavachari [J. Chem. Phys. 96, 2114 (1
992)], but some of the sequence bands observed within the progression
are not. We also observe transitions to the Si4 B-1(3u) state which is
found at a lower excitation energy than predicted. The perturbed vibr
ational structure in this band is attributed to vibronic coupling to a
nearby electronic state which is ''dark'' with respect to ZEKE spectr
oscopy. The ZEKE spectra are compared to the previously obtained photo
electron spectra of Si4- as well as ab initio calculations on Si4- and
Si4.