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

0181511 - UFCH-W 20020249 RIV US eng J - Journal Article
Roeselová, Martina - Mucha, Martin - Schmidt, B. - Jungwirth, Pavel
Quantum Dynamics and Spectroscopy of Electron Photodetachment in Cl-...H2O and Cl-...D2O Complexes.
Journal of Physical Chemistry A. Roč. 106, - (2002), s. 12229-12241. ISSN 1089-5639. E-ISSN 1520-5215
R&D Projects: GA MŠMT LN00A032
Institutional research plan: CEZ:AV0Z4040901
Keywords : water clusters * molecular dynamics * vibrational spectroscopy
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.765, year: 2002

We have modeled electron photodetachment 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 water rotation. These resonances form bands corresponding to water rotational states with a fine structure due to intermolecular stretch progressions.
Permanent Link: http://hdl.handle.net/11104/0001899