Complex potential energy surfaces with projected CAP technique: Vibrational excitation of N2.
| Autor: | Mondal S; Department of Chemistry, Boston University, Boston, Massachusetts 02215, USA., Bravaya KB; Department of Chemistry, Boston University, Boston, Massachusetts 02215, USA. |
|---|---|
| Jazyk: | angličtina |
| Zdroj: | The Journal of chemical physics [J Chem Phys] 2024 Jul 14; Vol. 161 (2). |
| DOI: | 10.1063/5.0212647 |
| Abstrakt: | The projected complex absorbing potential (CAP) technique is one of the methods that allow one to extend the bound state methods for computing resonances' energies and widths. Here, we explore the accuracy of the potential energy curves generated with different electronic structure theory methods in combination with the projected CAP technique by considering resonant vibrational excitation (RVE) of N2 by electron impact as a model process. We report RVE cross sections computed using the boomerang model with potential energy curves obtained with CAP-based extended multistate complete active space perturbation theory (XMS-CASPT2) and equation of motion coupled-cluster method for electron attachment with single and double substitution (EOM-EA-CCSD) methods. We also compare potential energy curves computed with several electronic structure methods, including XMS-CASPT2, EOM-EA-CCSD, multireference configuration interaction with singles (MR-CIS) and singles and doubles (MR-CISD). A good agreement is observed between the experiment and simulated RVE cross sections obtained with the potential energy curves generated with XMS-CASPT2 and EOM-EA-CCSD methods, thus highlighting the potential of the projected CAP technique combined with accurate electronic structure methods for dynamical simulations of the processes that proceed through metastable electronic states. (© 2024 Author(s). Published under an exclusive license by AIP Publishing.) |
| Databáze: | MEDLINE |
| Externí odkaz: |
|