10.1021/jp412564u.s001
Lucas
S. Rodríguez Pirani
Lucas
S. Rodríguez
Pirani
Mauricio F. Erben
Mauricio F.
Erben
Mariana Geronés
Mariana
Geronés
Rosana M. Romano
Rosana M.
Romano
Reinaldo L. Cavasso
Filho
Reinaldo L.
Cavasso
Filho
Chunping Ma
Chunping
Ma
Maofa Ge
Maofa
Ge
Carlos O. Della Védova
Carlos
O. Della Védova
Electronic Properties of FC(O)SCH<sub>2</sub>CH<sub>3</sub>. A Combined Helium(I) Photoelectron Spectroscopy and Synchrotron
Radiation Study
American Chemical Society
2014
HeI photoelectron spectrum
fragmentation
FC
S 2 p
OVGF
eV
region
quantum chemical calculations
HOMO
valence Green function method
synchrotron radiation
PEPICO
Synchrotron Radiation StudyThe valence
PEPIPICO
spectra
2014-08-07 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Electronic_Properties_of_FC_O_SCH_sub_2_sub_CH_sub_3_sub_A_Combined_Helium_I_Photoelectron_Spectroscopy_and_Synchrotron_Radiation_Study/2267002
The valence electronic properties
of <i>S</i>-ethyl flouromethanethioate
(<i>S</i>-ethyl fluoromethsanethioate), FC(O)SCH<sub>2</sub>CH<sub>3</sub>, were investigated by means of He(I) photoelectron
spectroscopy in conjunction with the analysis of the photofragmentation
products determined by PEPICO (phtoelectron-photoion-coincidence)
by using synchrotron radiation in the 11.1–21.6 eV photon energy
range. The first band observed at 10.28 eV in the HeI photoelectron
spectrum can be assigned with confidence to the ionization process
from the HOMO [n<sub>π</sub>(S) orbital], which is described
as a lone pair formally localized on the sulfur atom, in agreement
with quantum chemical calculations using the outer valence Green function
method [OVGF/6-311++G (d,p)]. One of the most important fragmentation
channels also observed in the valence region corresponds to the decarbonylation
process yielding the [M–CO]<sup>·+</sup> ion, which is
clearly observed at <i>m</i>/<i>z</i> = 80. Moreover,
S 2p and S 2s absorption edges have been examined by measuring the
total ion yield spectra in the 160–240 eV region using variable
synchrotron radiation. The dynamic of ionic fragmentation following
the Auger electronic decay has been evaluated with the help of the
PEPIPICO (photoion–photoion–photoelectron–coincidence
spectra) technique.