Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations
<jats:p> Knowledge of the chemical bonding of HfO and HfB ground and low-lying electronic states provides essential insights into a range of catalysts and materials that contain Hf–O or Hf–B moieties. Here, we carry out high-level multi-reference configuration interaction theory and coupled cl...
| Main Authors: | , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
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AIP Publishing
2022
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| Online Access: | https://hdl.handle.net/1721.1/145492 |
| _version_ | 1826215404234604544 |
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| author | Ariyarathna, Isuru R Duan, Chenru Kulik, Heather J |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Ariyarathna, Isuru R Duan, Chenru Kulik, Heather J |
| author_sort | Ariyarathna, Isuru R |
| collection | MIT |
| description | <jats:p> Knowledge of the chemical bonding of HfO and HfB ground and low-lying electronic states provides essential insights into a range of catalysts and materials that contain Hf–O or Hf–B moieties. Here, we carry out high-level multi-reference configuration interaction theory and coupled cluster quantum chemical calculations on these systems. We compute full potential energy curves, excitation energies, ionization energies, electronic configurations, and spectroscopic parameters with large quadruple- ζ and quintuple- ζ quality correlation consistent basis sets. We also investigate equilibrium chemical bonding patterns and effects of correlating core electrons on property predictions. Differences in the ground state electron configuration of HfB(X<jats:sup>4</jats:sup>[Formula: see text]<jats:sup>−</jats:sup>) and HfO(X<jats:sup>1</jats:sup>[Formula: see text]<jats:sup>+</jats:sup>) lead to a significantly stronger bond in HfO than HfB, as judged by both dissociation energies and equilibrium bond distances. We extend our analysis to the chemical bonding patterns of the isovalent HfX (X = O, S, Se, Te, and Po) series and observe similar trends. We also note a linear trend between the decreasing value of the dissociation energy (D<jats:sub>e</jats:sub>) from HfO to HfPo and the singlet–triplet energy gap ([Formula: see text]E<jats:sub>S–T</jats:sub>) of the molecule. Finally, we compare these benchmark results to those obtained using density functional theory (DFT) with 23 exchange–correlation functionals spanning multiple rungs of “Jacob’s ladder.” When comparing DFT errors to coupled cluster reference values on dissociation energies, excitation energies, and ionization energies of HfB and HfO, we observe semi-local generalized gradient approximations to significantly outperform more complex and high-cost functionals. </jats:p> |
| first_indexed | 2024-09-23T16:27:31Z |
| format | Article |
| id | mit-1721.1/145492 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T16:27:31Z |
| publishDate | 2022 |
| publisher | AIP Publishing |
| record_format | dspace |
| spelling | mit-1721.1/1454922022-09-29T19:56:00Z Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations Ariyarathna, Isuru R Duan, Chenru Kulik, Heather J Massachusetts Institute of Technology. Department of Chemistry Massachusetts Institute of Technology. Department of Chemical Engineering <jats:p> Knowledge of the chemical bonding of HfO and HfB ground and low-lying electronic states provides essential insights into a range of catalysts and materials that contain Hf–O or Hf–B moieties. Here, we carry out high-level multi-reference configuration interaction theory and coupled cluster quantum chemical calculations on these systems. We compute full potential energy curves, excitation energies, ionization energies, electronic configurations, and spectroscopic parameters with large quadruple- ζ and quintuple- ζ quality correlation consistent basis sets. We also investigate equilibrium chemical bonding patterns and effects of correlating core electrons on property predictions. Differences in the ground state electron configuration of HfB(X<jats:sup>4</jats:sup>[Formula: see text]<jats:sup>−</jats:sup>) and HfO(X<jats:sup>1</jats:sup>[Formula: see text]<jats:sup>+</jats:sup>) lead to a significantly stronger bond in HfO than HfB, as judged by both dissociation energies and equilibrium bond distances. We extend our analysis to the chemical bonding patterns of the isovalent HfX (X = O, S, Se, Te, and Po) series and observe similar trends. We also note a linear trend between the decreasing value of the dissociation energy (D<jats:sub>e</jats:sub>) from HfO to HfPo and the singlet–triplet energy gap ([Formula: see text]E<jats:sub>S–T</jats:sub>) of the molecule. Finally, we compare these benchmark results to those obtained using density functional theory (DFT) with 23 exchange–correlation functionals spanning multiple rungs of “Jacob’s ladder.” When comparing DFT errors to coupled cluster reference values on dissociation energies, excitation energies, and ionization energies of HfB and HfO, we observe semi-local generalized gradient approximations to significantly outperform more complex and high-cost functionals. </jats:p> 2022-09-19T16:53:10Z 2022-09-19T16:53:10Z 2022 2022-09-19T16:41:47Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/145492 Ariyarathna, Isuru R, Duan, Chenru and Kulik, Heather J. 2022. "Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations." The Journal of Chemical Physics, 156 (18). en 10.1063/5.0090128 The Journal of Chemical Physics Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf AIP Publishing American Institute of Physics (AIP) |
| spellingShingle | Ariyarathna, Isuru R Duan, Chenru Kulik, Heather J Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations |
| title | Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations |
| title_full | Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations |
| title_fullStr | Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations |
| title_full_unstemmed | Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations |
| title_short | Understanding the chemical bonding of ground and excited states of HfO and HfB with correlated wavefunction theory and density functional approximations |
| title_sort | understanding the chemical bonding of ground and excited states of hfo and hfb with correlated wavefunction theory and density functional approximations |
| url | https://hdl.handle.net/1721.1/145492 |
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