Modeling Photoelectron Spectra of CuO, Cu2O, and CuO2 Anions with Equation-of-Motion Coupled-Cluster Methods: An Adventure in Fock Space
| Autor: | Natalie Orms, Anna I. Krylov |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Copper oxide
010304 chemical physics Chemistry Triatomic molecule Electronic structure 010402 general chemistry 01 natural sciences Molecular physics 0104 chemical sciences Fock space Pseudopotential chemistry.chemical_compound Coupled cluster Atomic orbital Condensed Matter::Superconductivity 0103 physical sciences Physics::Atomic and Molecular Clusters Physics::Chemical Physics Physical and Theoretical Chemistry Basis set |
| Zdroj: | The Journal of Physical Chemistry A. 122:3653-3664 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.7b10620 |
| Popis: | The experimental photoelectron spectra of di- and triatomic copper oxide anions have been reported previously. We present an analysis of the experimental spectra of the CuO–, Cu2O–, and CuO2– anions using equation-of-motion coupled-cluster (EOM-CC) methods. The open-shell electronic structure of each molecule demands a unique combination of EOM-CC methods to achieve an accurate and balanced representation of the multiconfigurational anionic- and neutral-state manifolds. Analysis of the Dyson orbitals associated with photodetachment from CuO– reveals the strong non-Koopmans character of the CuO states. For the lowest detachment energy, a good agreement between theoretical and experimental values is obtained with CCSD(T) (coupled-cluster with single and double excitations and perturbative account of triple excitations). The (T) correction is particularly important for Cu2O–. Use of a relativistic pseudopotential and matching basis set improves the quality of results in most cases. EOM-DIP-CCSD analysis of t... |
| Databáze: | OpenAIRE |
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