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J Chem Phys. 2004 Oct 8;121(14):6628-33.

Extrapolating bound state data of anions into the metastable domain.

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Theoretische Chemie, Physikalisch-Chemisches Institut Universit├Ąt Heidelberg Im Neuenheimer Feld 229, 69120 Heidelberg, Germany.


Computing energies of electronically metastable resonance states is still a great challenge. Both scattering techniques and quantum chemistry based L2 methods are very time consuming. Here we investigate two more economical extrapolation methods. Extrapolating bound states energies into the metastable region using increased nuclear charges has been suggested almost 20 years ago. We critically evaluate this attractive technique employing our complex absorbing potential/Green's function method that allows us to follow a bound state into the continuum. Using the (2)Pi(g) resonance of N2- and the (2)Pi(u) resonance of CO2- as examples, we found that the extrapolation works suprisingly well. The second extrapolation method involves increasing of bond lengths until the sought resonance becomes stable. The keystone is to extrapolate the attachment energy and not the total energy of the system. This method has the great advantage that the whole potential energy curve is obtained with quite good accuracy by the extrapolation. Limitations of the two techniques are discussed.


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