The near-edge X-ray absorption fine structure (NEXAFS) spectra
were studied at the S K-edge using
synchrotron radiation for various sulfur-containing organic
photographic materials in the solid state and in
the adsorbed states on AgCl and AgBr grains. The features in the
spectra of neat solids were assigned by
mutual comparison and polarization dependence. The spectra of
merocyanine dyes containing thiocarbonyl
group were drastically affected by the adsorption on AgCl and AgBr,
with significant suppression of the
peak corresponding to the excitation of the S 1s electron into the π*
orbital at the SC bond. This change
is interpreted as indicative that these compounds are adsorbed at the S
atom in the thiocarbonyl group, such
rearrangement of the chemical bonds leading to a contribution from the
zwitterionic form with
S-−CN+<
structure. By taking account of the area occupied by a molecule
estimated from the measurements of the
adsorption isotherm, a rather detailed picture emerged about the
adsorbed state of this kind of dye. In contrast,
the spectra of merocyanine and cyanine dyes containing sulfur in the
five-membered aromatic ring showed
little change by the adsorption on AgCl, indicating that the S atom is
not the adsorption site or that the
interaction between the molecule and AgCl is weak.