Charge-partition pathways in strong-field photoionization of carbonyl sulfide monomers and dimers

Abstract

Strong-field photoionization of molecules and molecular clusters gives rise to a rich variety of fragmentation pathways governed by charge localization and redistribution on ultrafast timescales. Here, we report a velocity-map imaging study of the strong-field photoionization and fragmentation of carbonyl sulfide (OCS) monomers and dimers driven by 150 femtosecond (fs) laser pulses at 775~nm. The images of the total kinetic-energy and angular distributions of the OCS$^{2+}$, S$^+$, and CO$^+$ fragments were interpreted with the help of electronic-structure calculations of the potential energy surfaces for OCS$^+$ and OCS$^{2+}$. We identify distinct dissociation pathways of singly and doubly ionized OCS, including two-body breakup channels of OCS$^+$ into $\mathrm{S}^+ + \mathrm{CO}$ and $\mathrm{CO}^+ + \mathrm{S}$, dissociation of OCS$^{2+}$ into $\mathrm{S}^+ + \mathrm{CO}$$^+$ as well as higher-order three-body fragmentation. In addition, the images of the OCS$^{2+}$ channel exhibit near-zero-momentum components, low-energy isotropic features, and highly anisotropic contributions at high kinetic energies that cannot be explained by monomer ionization alone. Analysis of the KER distributions and angular anisotropies indicates that these features originate from the breakup of multiply charged OCS dimers ((OCS)$_2^{2+}$, (OCS)$_2^{3+}$, and (OCS)$_2^{4+}$) through charge-separation channels. Our results illustrate how dynamic signatures of strong-field fragmentation evolve from intramolecular dissociation in isolated molecules to intermolecular charge separation in weakly bound clusters providing a unified picture of charge-driven dissociation dynamics beyond the single-molecule limit.