E×e Jahn–Teller effect in the P4+ cation and its signatures in the photoelectron spectrum of P4
| Autor: | Swarnendu Bhattacharyya, Daniel Opalka, Wolfgang Domcke |
|---|---|
| Rok vydání: | 2015 |
| Předmět: |
Condensed matter physics
Chemistry Photoemission spectroscopy Jahn–Teller effect Anharmonicity Ab initio General Physics and Astronomy Molecular physics Potential energy Normal mode Physics::Atomic and Molecular Clusters Condensed Matter::Strongly Correlated Electrons Physical and Theoretical Chemistry Ground state Basis set |
| Zdroj: | Chemical Physics. 460:51-55 |
| ISSN: | 0301-0104 |
| DOI: | 10.1016/j.chemphys.2015.05.002 |
| Popis: | The Jahn–Teller effect in the electronic ground state of the P 4 + radical cation, which is one of the strongest E × e Jahn–Teller effects known in nature, has been revisited in this work with computational methods. The relevance of the Jahn–Teller coupling terms beyond second order in normal-mode displacements has been investigated. An elegant and efficient scheme based on polynomial invariant theory has been employed to expand the E × e potential energy matrix up to arbitrarily high orders in normal mode displacements. Using the state-averaged complete-active-space self-consistent-field method and a correlation consistent double- ζ basis set, an accurate ab initio adiabatic E × e Jahn–Teller potential-energy surface was obtained. It is shown that a polynomial expansion of least up to sixth order is necessary to account for the pronounced anharmonicity of the ab initio potential-energy surface for large amplitude displacements of the Jahn–Teller active vibrational mode. The vibronic structure of the X 2 E band of the photoelectron spectrum of P 4 has been computed using a time-dependent wave-packet propagation method. The results reveal the significance of the higher-order Jahn–Teller coupling terms for the high-resolution vibronic spectrum as well as for the low-resolution band shape. |
| Databáze: | OpenAIRE |
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