Refine
Has Fulltext
- no (26)
Year of publication
Document Type
- Article (21)
- Monograph/Edited Volume (5)
Is part of the Bibliography
- yes (26)
Institute
- Institut für Chemie (26)
The geometric structure and bonding properties of medium-sized ArnH+ clusters (n = 2-35), in which a proton is wrapped up in a number of Ar atoms, are investigated by applying a diatomics-in-molecules (DIM) model with ab-initio input data generated by means of multi-reference configuration-interaction (MRCI) computations. For the smaller complexes, n = 2-7, cross-checking calculations employing the coupled-cluster approach (CCSD) with the same one-electron atomic basis set as for the input data calculations (aug-cc-pVTZ from Dunning), show good agreement thus justifying the extension of the DIM study to larger n. Local minima of the multi-dimensional potential-energy surfaces (PES) are determined by combining a Monte-Carlo sampling followed, for each generated point, by a steepest-descent optimization procedure. For the electronic ground state of the ArnH+ clusters, the global minimum (corresponding to the most stable structure of the cluster) as well as secondary minima are found and analyzed. The structural and energetic data obtained reveal the building-up regularities for the most stable structures and make it possible to formulate a simple increment scheme. The low-lying excited states are also calculated by the DIM approach; they all turn out to be globally repulsive
The electronic and geometric structure, stability and molecular properties of the cationic van-der-Waals complex Ar2H+ in its ground electronic state are studied by means of two ab-initio quantum-chemical approaches: conventional configuration interaction (multi-reference and coupled cluster methods) and a diatomics-in-molecules model with ab-initio input data.
Motivated by the possible importance of OBrO in atmospheric photochemistry, multireference configuration interaction calculations of the low-lying excited states were carried out to obtain information about the electronic vertical spectrum up to excitation energies of about 6 eV from the ground state, including the transition dipole moments, and about possible photodissociation pathways, based on one-dimensional cuts through the potential energy surfaces for dissociation into BrO + O and Br + O2, respectively. In addition, for probing the angle dependence the bending potentials were also calculated.