| Autor: |
Moorby, Robin E., Parravicini, Valentina, Alessio, Maristella, Jagau, Thomas-C. |
| Zdroj: |
Physical Chemistry Chemical Physics (PCCP); 2/28/2024, Vol. 26 Issue 8, p6532-6539, 8p |
| Abstrakt: |
We compute EOM-EA-CCSD and EOM-EA-CCSDT potential energy curves and one-electron properties of several anions at bond lengths close to where these states become unbound. We compare the anions of HCl and pyrrole, which are associated with s-wave scattering, with N2 and H2, which correspond to resonances. For HCl and pyrrole, we observe, on inclusion of diffuse basis functions, a pronounced bending effect in the anionic potential energy curves near the crossing points with their corresponding neutral molecules. Additionally, we observe that the Dyson orbital and second moment of the electron density become extremely large in this region; for HCl, the size of the latter becomes 5 orders of magnitude larger over a range of 5 pm. This behaviour is not observed in H2 or N2. Our work thus shows that bound state electronic-structure methods can distinguish between anions that turn into electronic resonances and those associated with s-wave scattering states. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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