Quantum Dynamics and Spectroscopy of Electron Photodetachment in Cl-…H2O and Cl-…D2O Complexes

Optimal structures of Cl-…H2O complex:(a) anionic complex; (b) neutral complex; (c) C2v symmetric geometry

Martina Roeselová, Martin Mucha, Burkhard Schmidt, and Pavel Jungwirth

We have modeled Zero Electron Kinetic Energy (ZEKE) spectra of Cl-…H2O and Cl-…D2O complexes using 3D quantum dynamical simulations on the three low-lying electronic states of the nascent neutral systems. Time-dependent quantum simulations combined with anionic and neutral stationary-state calculations by imaginary time propagation allowed for a detailed interpretation of the spectral features in terms of the underlying dynamics. Because of large differences between the anionic and neutral potential surfaces, the systems are found after electron photodetachment primarily high above the dissociation threshold. Nevertheless, pronounced long-lived resonances are observed, particularly for the lowest neutral state, reflecting the fact that a significant portion of the excess energy is initially deposited into nondissociative modes, that is, to (hindered) water rotation. These resonances form bands corresponding to water rotational states with a fine structure due to intermolecular stretch progressions. Comparison is made to experimental zero electron kinetic energy (ZEKE) spectra of the I-…H2O complex, where analogous anharmonic vibrational progressions have been observed.

J. Phys. Chem. A 106 (51), 12229-12241 (2002)