The VUV Absorption Spectra of SiF and SiF+

Extensive theoretical study on the low‐lying electronic states of silicon monofluoride cation including spin‐orbit coupling

“…16 Our computed vertical IP of X 2 P SiF to A 1 P SiF þ (7r??) is 14.62 eV, and is larger than that obtained by Karna and Grein, 24 but is still lower than the experimental value reported by Bredohl et al 17 This difference may be partially caused by the blue-shift of the absorption peak of A state of SiF þ in Figure 1 of ref. 17.…”

“…In 1996, Reid 16 obtained the a 3 P cationic state energies and adiabatic electron affinities of SiF by translationalenergy spectroscopy. More recently, Bredohl et al 17 observed three bands with the ionization potentials of 7.31 6 0.02, 15.12 6 0.12, and 17.27 6 0.13 eV, respectively in their study of the vacuum ultraviolet absorption spectra of SiF, which were assigned to three electronic states of SiF þ . However, the experi-Previous theoretical studies of SiF þ concentrated on its ground state [18][19][20][21][22][23] and the first excited state (a 3 P), 22,23 and the only calculational work that involved several excited states was performed by Karna and Grein.…”

Halogenated silanes, radicals, and cations: Theoretical predictions on ionization energies, structures and potential energy surfaces of cations, proton affinities, and enthalpies of formation

“…Two IEs each were reported for SiF (7.54 ± 0.16 eV [40] or 7.08 ± 0.10 eV [41]) and SiCl (7.44 ± 0.40 eV [43] and 6.79 ± 0.24 eV [44]). Alternatively, IE a (SiF) of 7.31 ± 0.02 eV from VUV Rydberg spectra [32] was supported by theoretical predictions of 7.21 eV at MP4/6-31G(d,p) level [29], 7.36 eV at CCSD(T)/CBS level [54], and 7.41 eV at G3(CC) level. For IE a (SiCl), Bosser et al [33] have estimated value of 6.82 eV from only two Rydberg states, and later revised it to 7.368 eV with more Rydberg states [34].…”

“…Present G3(CC) represents the first systematic study on this system. G3(CC) calculations show strong effects from F-substitution with increased IE a from SiH 2 F (8.12 eV) to SiF 3 (9.17 eV), very small effect from Cl- Values are obtained from: a JANAF table [94]; b photoionization [31]; c Ion chemistry [38]; d BAC-MP4/6-31G(d,p) [29]; e Ion chemistry [40]; f Ion chemistry [41]; g Rydberg series [32]; h CCSD(T)/CBS [54]; i Ion chemistry [43]; j Ion chemistry [44]; k Rydberg series [33]; l Photoionization mass spectrometry [35]; m CCSD(T)/AVQZ calculation [51]; n Electron impact ionization [76]; o Rydberg series [37]; p Photoelectron spectroscopy [72]; q CCSD(T)/CBS [60]; r Electron impact ionization [73]; s Photoelectron spectroscopy [74]; t G2(MP2) calculation [51]; u Estimation from photoionization [75]; v Rydberg series [36]; w Photoelectron spectroscopy [78]; x Ion-molecule reaction [45,46]; y Estimation from photoelectron spectroscopy [77]. substitution with small change of IE a from SiH 2 Cl (7.90 eV) to SiCl 3 (7.85 eV), and from Br-substitution with slightly decreased IE a from SiH 2 Br (7.83 eV) to SiBr 3 (7.63 eV).…”

“…Reliable measurements on IE a were available only to SiH x 0,+1 (x = 1-4) from photoionization mass spectrometry study by Berkowitz et al [31]. There were also reports on IE a (SiX, X = F,Cl,Br) from photoionization efficiency spectroscopy or VUV spectroscopy of Rydberg states [32][33][34][35][36][37].…”