Do Dyson Orbitals resemble canonical Hartree–Fock orbitals?

Díaz–Tinoco, Manuel; Corzo, Héctor H.; Pawłowski, Filip; Ortiz, J. V.

doi:10.1080/00268976.2018.1535142

Cited by 34 publications

(31 citation statements)

References 32 publications

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“…For best accuracy, Dyson orbitals should be calculated from fully correlated wave functions, but it is informative to consider calculating them in the HF approximation, which one might hope to give a good approximation for weakly correlated molecules. If one uses the HF approximation for Ψ N and Ψ N −1 and one makes the approximations described above leading to Koopmans’ theorem, then the Dyson orbital becomes a canonical HF orbital, and comparisons of canonical HF orbitals to Dyson orbitals have shown this to be a good approximation for some simple molecules . But, even when this is a good approximation, it should not be interpreted as saying that the experiment showed that the electrons in the neutral molecule are in a particular kind of orbital prior to the ionization event.…”

Section: Dyson Orbitals: Theory and Experimentsmentioning

confidence: 99%

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

et al. 2019

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Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopyp rovide unique information about electronic structure,b ut their interpretation has been controversial. This essay discusses aframework for interpretation. Although this interpretation is not new,webelieve it is important to present this framework in light of recent publications.T he key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre-ionized state.T herefore,t hese experiments do not lead to a"selection of the correct orbitals" in chemistry and do not overturn the well-known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties.Different types of orbitals are useful for different purposes.

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Section: Dyson Orbitals: Theory and Experimentsmentioning

confidence: 99%

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

et al. 2019

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“…How, then, do we account for the success of qualitative MO theory if it is based on fictitious one-electron wave functions? The answer is that the commonly used Hartree-Fock MOs strongly resemble Dyson orbitals [31] which are real and measurable [32]. This observation provides a link between MO theory and real observables, so that qualitative MO theory is a widely used and successful approach to understanding chemical structures and reactivity.…”

Section: Molecular Orbitalsmentioning

confidence: 99%

Models of necessity

Clark¹,

Hicks²

2020

Beilstein J. Org. Chem.

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The way chemists represent chemical structures as two-dimensional sketches made up of atoms and bonds, simplifying the complex three-dimensional molecules comprising nuclei and electrons of the quantum mechanical description, is the everyday language of chemistry. This language uses models, particularly of bonding, that are not contained in the quantum mechanical description of chemical systems, but has been used to derive machine-readable formats for storing and manipulating chemical structures in digital computers. This language is fuzzy and varies from chemist to chemist but has been astonishingly successful and perhaps contributes with its fuzziness to the success of chemistry. It is this creative imagination of chemical structures that has been fundamental to the cognition of chemistry and has allowed thought experiments to take place. Within the everyday language, the model nature of these concepts is not always clear to practicing chemists, so that controversial discussions about the merits of alternative models often arise. However, the extensive use of artificial intelligence (AI) and machine learning (ML) in chemistry, with the aim of being able to make reliable predictions, will require that these models be extended to cover all relevant properties and characteristics of chemical systems. This, in turn, imposes conditions such as completeness, compactness, computational efficiency and non-redundancy on the extensions to the almost universal Lewis and VSEPR bonding models. Thus, AI and ML are likely to be important in rationalizing, extending and standardizing chemical bonding models. This will not affect the everyday language of chemistry but may help to understand the unique basis of chemical language.

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“…How, then, do we account for the success of qualitative MO-theory if it is based on fictitious oneelectron wavefunctions? The answer is that the commonly used Hartree-Fock MOs strongly resemble Dyson orbitals [30] which are real and measurable [31]. This observation provides a link between MO-theory and real observables, so that qualitative MO theory is a widely used and successful approach to understanding chemical structures and reactivity.…”

Section: Molecular Orbitalsmentioning

confidence: 99%

Models of Necessity

Clark¹,

Hicks²

2020

Preprint

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The everyday language of chemistry uses models, particularly of bonding, that are not contained in the quantum mechanical description of chemical systems. To date, this everyday language has overlapped strongly with that (the ontology) of artificial intelligence (AI) and machine learning (ML). Within the everyday language, the model nature of these concepts is not always clear to practicing chemists, so that controversial discussions about the merits of alternative models often arise. However, the extensive use of AI and ML in chemistry will require that these models be extended to cover all relevant properties and characteristics of chemical systems. This in turn imposes conditions such as completeness, compactness, computational efficiency and non-redundancy on the extensions to the almost universal Lewis and VSEPR bonding models. Thus, AI and ML are likely to be important in rationalizing and standardizing chemical bonding models. This will not affect the everyday language of chemistry but may help understand the unique basis of chemical language.

show abstract

Do Dyson Orbitals resemble canonical Hartree–Fock orbitals?

Cited by 34 publications

References 32 publications

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Models of necessity

Models of Necessity

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