Threshold photodetachment zero-electron kinetic energy spectroscopy of Si−3

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Abstract
The threshold photodetachment zero‐electron kinetic energy (ZEKE) spectrum of Si− 3 is presented and discussed. The spectrum shows well‐resolved vibrational structure. A comparison with several ab initio calculations shows that the spectrum is due to transitions to the 3 A ’ 2 (D 3h ) state of Si3. The symmetric stretch and degenerate e’ frequencies for the Si3 3 A ’ 2 state are determined to be 501±10 and 337±10 cm−1, respectively. Additional structure observed in the spectrum suggests that the negative ion is a fluxional, Jahn–Teller distorted species. The ZEKE spectrum shows no evidence for transitions to the 1 A 1 state of the neutral, which is predicted to lie very close to the 3 A ’ 2 state. A comparison of the ZEKE and previously obtained photoelectron spectrum of Si− 3 suggests that these two states are close in energy, but that transitions to the singlet state are very weak in the ZEKE spectrum.

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