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The impact of the solvent on the photodissociation of embedded molecules has been intensively investigated in the last decades. Collisions of photofragments with the solvating atoms or molecules can change their kinetic energy distribution or even lead to the de-excitation of the dissociating molecule to a bound electronic state quenching the dissociation. In this article we show that this cage effect is strongly enhanced if interatomic Coulombic decay (ICD) of the excited state becomes allowed. Ab initio calculations in H2O-Cl- cluster show that the ultra-fast dissociation of water in the à excited state is strongly quenched by ICD. We found that this very efficient quenching is due to two factors. First, the lifetimes of the ÃA state due to ICD are short ranging between 6 and 30 fs. Second, nuclear dynamics is dominated by the chattering motion of the H atom between O and Cl- allowing ICD to act for longer times. We hope that this work will be an important first step in clarifying the impact of ICD on photodissociation of embedded molecules. [ABSTRACT FROM AUTHOR]

For computational rovibrational spectroscopy the choice of the frame is critical for an approximate separation of overall rotation from internal motions. To minimize the coupling between internal coordinates and rotation, Eckart proposed a condition [“Some studies concerning rotating axes and polyatomic molecules," Phys. Rev.47, 552–558 (1935)] and a frame that fulfills this condition is hence called an Eckart frame. A method is developed to introduce in a systematic way the Eckart frame for the expression of the kinetic energy operator (KEO) in the polyspherical approach. The computed energy levels of a water molecule are compared with those obtained using a KEO in the standard definition of the Body-fixed frame of the polyspherical approach. The KEO in the Eckart frame leads to a faster convergence especially for large J states and vibrationally excited states. To provide an example with more degrees of freedom, rotational states of the vibrational ground state of the trans nitrous acid (HONO) are also investigated. [ABSTRACT FROM AUTHOR]

Generalized curvilinear coordinates, as, e.g., polyspherical coordinates, are in general better adapted to the resolution of the nuclear Schrödinger equation than rectilinear ones like the normal mode coordinates. However, analytical expressions of the kinetic energy operators (KEOs) for molecular systems in polyspherical coordinates may be prohibitively complicated for large systems. In this paper we propose a method to generate a KEO numerically and bring it to a form practicable for dynamical calculations. To examine the new method we calculated vibrational spectra and eigenenergies for nitrous acid (HONO) and compare it with results obtained with an exact analytical KEO derived previously [F. Richter, P. Rosmus, F. Gatti, and H.-D. Meyer, J. Chem. Phys. 120, 6072 (2004)]. In a second example we calculated π → π* photoabsorption spectrum and eigenenergies of ethene (C2H4) and compared it with previous work [M. R. Brill, F. Gatti, D. Lauvergnat, and H.-D. Meyer, Chem. Phys. 338, 186 (2007)]. In this ethene study the dimensionality was reduced from 12 to 6 by freezing six internal coordinates. Results for both molecules show that the proposed method for obtaining an approximate KEO is reliable for dynamical calculations. The error in eigenenergies was found to be below 1 cm-1 for most states calculated. [ABSTRACT FROM AUTHOR]