ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Theoretical investigations of the outer valence doubly ionized states of ethylene are presented using ab initio Green's function and configuration interaction methods. The vertical double ionization potentials computed by the Green's function method using the ADC(2) scheme are discussed in connection with the Auger spectrum of ethylene and found to reproduce the experimental spectrum quite accurately. Another main purpose of the present work is the investigation of the potential energy surfaces of selected states via ADC(2) and the study of the nuclear dynamics on them. It is shown that only the ground state of the dication is nonplanar with a torsional angle of 90°. The investigation of the topology of the surfaces reveals a low energy conical intersection of the dicationic ground and first excited states. The associated vibronic coupling problem turns out to include, additionally, the second excited state and thus, we encounter here a three-state problem. In the approximation of linear vibrational and vibronic coupling the static and dynamic aspects of the vibronic interaction are investigated by a model Hamiltonian comprising three nonseparable nondegenerate vibrational modes. The input data for the model are extracted from the ADC(2) results. With the aid of this Hamiltonian we have computed a hypothetical "sudden'' double ionization spectrum of ethylene whose complex structure is analyzed stepwise and by cuts through the pertinent adiabatic and diabatic surfaces. The analysis exhibits that the conical intersection of the two lower lying states dominates the vibronic dynamics and leads to strong vibronic mixing between them. This mixing is indirectly reinforced by the interaction between the intermediate and the upper states. As a consequence, strong nonadiabatic effects occur in the ethylene dication. Furthermore, two of the three surfaces involved in the conical intersection are also involved in a multidimensional avoided crossing. A more detailed analysis presented earlier has exhibited that the states belong to an interesting class where two potential energy surfaces are likely not to coincide although plenty of nuclear degrees of freedom exist, in principle, to allow for an intersection to occur.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.457080
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