Enhancing the Accuracy of XPS Calculations: Exploring Hybrid Basis Set Schemes for CVS-EOMIP-CCSD Calculations
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arXiv
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| Formato: | Preprint |
| Publicado: |
2024
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| _version_ | 1866910891010686976 |
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| author | Delgado, Alexis A. A. Matthews, Devin A. |
| author_facet | Delgado, Alexis A. A. Matthews, Devin A. |
| contents | Reliable computational methodologies and basis sets for modeling x-ray spectra are essential for extracting and interpreting electronic and structural information from experimental x-ray spectra. In particular, the trade-off between numerical accuracy and computational cost due to the size of the basis set is a major challenge, since molecular orbitals undergo extreme relaxation in the core-hole state. To gain clarity on changes in electronic structure induced by the formation of a core-hole, the use of sufficiently flexible basis for expanding the orbitals, particularly for the core region, has been shown to be essential. This work focuses on the refinement of core-hole ionized state calculations using the equation-of-motion coupled cluster (EOM-CC) family of methods through an extensive analysis on the effectiveness of "hybrid" and mixed basis sets. In this investigation, we utilize the CVS-EOMIP-CCSD method in combination and construct hybrid basis sets piece-wise from readily available Dunning's correlation consistent basis sets in order to calculate x-ray ionization energies for a set of small gas phase molecules. Our results provide insights into the impact of basis sets on CVS-EOMIP-CCSD calculations of K-edge ionization energies of first-row p-block elements. These insights enable us to understand more about the basis set dependence of the core IEs computed and allow us to establish a protocol for deriving reliable and cost-effective theoretical estimates for computing IEs of small molecules containing such elements. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2411_03492 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Enhancing the Accuracy of XPS Calculations: Exploring Hybrid Basis Set Schemes for CVS-EOMIP-CCSD Calculations Delgado, Alexis A. A. Matthews, Devin A. Chemical Physics Reliable computational methodologies and basis sets for modeling x-ray spectra are essential for extracting and interpreting electronic and structural information from experimental x-ray spectra. In particular, the trade-off between numerical accuracy and computational cost due to the size of the basis set is a major challenge, since molecular orbitals undergo extreme relaxation in the core-hole state. To gain clarity on changes in electronic structure induced by the formation of a core-hole, the use of sufficiently flexible basis for expanding the orbitals, particularly for the core region, has been shown to be essential. This work focuses on the refinement of core-hole ionized state calculations using the equation-of-motion coupled cluster (EOM-CC) family of methods through an extensive analysis on the effectiveness of "hybrid" and mixed basis sets. In this investigation, we utilize the CVS-EOMIP-CCSD method in combination and construct hybrid basis sets piece-wise from readily available Dunning's correlation consistent basis sets in order to calculate x-ray ionization energies for a set of small gas phase molecules. Our results provide insights into the impact of basis sets on CVS-EOMIP-CCSD calculations of K-edge ionization energies of first-row p-block elements. These insights enable us to understand more about the basis set dependence of the core IEs computed and allow us to establish a protocol for deriving reliable and cost-effective theoretical estimates for computing IEs of small molecules containing such elements. |
| title | Enhancing the Accuracy of XPS Calculations: Exploring Hybrid Basis Set Schemes for CVS-EOMIP-CCSD Calculations |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2411.03492 |