Spin- and angle-resolved spectroscopy of $\mathrm{S}2p$ photoionization in the hydrogen sulfide molecule

Angle- and spin-resolved photoelectron spectroscopy with circularly and linearly polarized synchrotron radiation were used to study the electronic structure of the hydrogen sulfide molecule. A strong effect of the molecular environment appears in the spin-resolved measurements and, although less clearly, in the angular distribution of the sulfur $2p$ photoelectrons. The anisotropy and spin parameters of the three main spectral components have been obtained. The validity of simple atomic models in explaining the results is discussed.

Figure 1

Photoionization spectrum of $\mathrm{Kr}$ $3d$ (top) and $\mathrm{S}2p$ shell of ${\mathrm{H}}_2\mathrm{S}$ (bottom) as measured at the magic angle with $200\mathrm{eV}$ linearly polarized light. The continuous and dashed curves are the result of a least-squares fitting procedure. Lines labeled $A,B$, and $C$ in the bottom panel are associated with the ${\mathrm{H}}_2\mathrm{S}$ ion in its ground vibrational state.

Figure 2

$\mathrm{S}2p$ photoionization spectra as measured with $210\mathrm{eV}$ linearly polarized light. Bottom: total intensity; the continuous curves are the result of a least-squares fitting procedure. Middle: spin-resolved spectra (spin parallel $◻$ and antiparallel $▾$ to the photon propagation). Top: spin polarization, calculated from the peak areas $●$and the individual data points $엯$.

Figure 3

Anisotropy parameter as a function of the photoelectron kinetic energy. Experimental points are for the ground vibrational state of $\left(\ast =A\right)\mathrm{S}2p_{1∕2}$ and $\left(●=B,엯=C\right)$ molecular field split $\mathrm{S}2p_{3∕2}$ in the lower panel, and for the unresolved doublet $2p_{3∕2}(◻)$ in the upper panel. Full lines are calculations for $\mathrm{Ar}2p$ photoionization.

Figure 4

Spin polarization as a function of the photoelectron kinetic energy as measured with linearly polarized light. Experimental points are for the ground vibrational state of $\left(\ast =A\right)\mathrm{S}2p_{1∕2}$, lower panel, and $\left(●=B,엯=C\right)$ molecular field split $\mathrm{S}2p_{3∕2}$ and unresolved doublet $2p_{3∕2}(◻)$, upper panel. Full lines are calculations for $\mathrm{Ar}2p$ photoionization.

Figure 5

Same as Fig. 4, as measured with circularly polarized light.