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Title: spin-coupled molecular orbitals: chemical intuition meets quantum chemistry.

Abstract: Molecular orbital theory is powerful both as a conceptual tool for understanding chemical bonding, and as a theoretical framework for ab initio quantum chemistry. Despite its undoubted success, MO theory has well documented shortcomings, most notably that it fails to correctly describe diradical states and homolytic bond fission. In this contribution, we introduce a generalised MO theory that includes spin-coupled radical states. We show through archetypical examples that when bonds break, the electronic state transitions between a small number of valence configurations, characterised by occupation of both delocalised molecular orbitals and spin-coupled localised orbitals. Our theory provides a model for chemical bonding that is both chemically intuitive and qualitatively accurate when combined with ab initio theory. Although exploitation of our theory presents significant challenges for classical computing, the predictable structure of spin-coupled states is ideally suited to algorithms that exploit quantum computers. Our approach provides a systematic route to overcoming the initial state overlap problem and unlocking the potential of quantum computational chemistry.

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Perspective on “New developments in molecular orbital theory”

Roothaan CCJ (1951) Rev Mod Phys 23: 69–89

• Perspective
• Published: February 2000
• Volume 103 , pages 217–218, ( 2000 )

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• Michael C. Zerner 1  

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This paper reviews the title article by Clemens Roothaan and the huge impact that his paper has had in modern chemistry. In his paper Roothaan converts the molecular Schödinger equation into a matrix equation by systematically introducing the linear combination of atomic orbitals–molecular orbital approximation and by invoking the variational principle.

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Quantum Theory Project, Department of Chemistry, University of Florida, Gainesville, FL 32611, USA, , , , , , US

Michael C. Zerner

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Received: 12 February 1999 / Accepted: 26 February 1999 / Published online: 7 June 1999

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Zerner, M. Perspective on “New developments in molecular orbital theory”. Theor Chem Acc 103 , 217–218 (2000). https://doi.org/10.1007/s002149900010

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Issue Date : February 2000

DOI : https://doi.org/10.1007/s002149900010

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• Key words: Roothaan equation – Roothaan–Hall – Hartree–Fock – Roothaan self-consistent field
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Valence bond theory—its birth, struggles with molecular orbital theory, its present state and future prospects.

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1. Introduction

2. the roots and development of vb theory, 2.1. the lewis electronic cubes and electron pair bonds, 2.2. heitler, london, pauling and slater, and the development of vb theory: heitler and london’s study and follow-ups, 2.3. pauling and slater, 3. origins of mo theory, 4. the mo–vb “wars”, 5. hybridization is being called into doubt, 6. conceptual errors made during the early development of vb theory, 6.1. assessment of the covalent–ionic bond scheme, 6.2. missing the antiaromatic character of c 4 h 4, 7. myths about vb failures, 7.1. the o 2 myth and mystery, 7.2. the myth of the photoelectron spectroscopies (pes) of ch 4 and h 2 o, 8. modern vb theory, modern quantitative vbt approaches, 9. modern conceptual approaches in vbt, 10. vb-motivated approaches, 11. conclusions, author contributions, institutional review board statement, informed consent statement, data availability statement, acknowledgments, conflicts of interest.

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Shaik, S.; Danovich, D.; Hiberty, P.C. Valence Bond Theory—Its Birth, Struggles with Molecular Orbital Theory, Its Present State and Future Prospects. Molecules 2021 , 26 , 1624. https://doi.org/10.3390/molecules26061624

Shaik S, Danovich D, Hiberty PC. Valence Bond Theory—Its Birth, Struggles with Molecular Orbital Theory, Its Present State and Future Prospects. Molecules . 2021; 26(6):1624. https://doi.org/10.3390/molecules26061624

Shaik, Sason, David Danovich, and Philippe C. Hiberty. 2021. "Valence Bond Theory—Its Birth, Struggles with Molecular Orbital Theory, Its Present State and Future Prospects" Molecules 26, no. 6: 1624. https://doi.org/10.3390/molecules26061624

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• DOI: 10.1063/1.1740412
• Corpus ID: 94740146

Molecular Orbital Theory of Orientation in Aromatic, Heteroaromatic, and Other Conjugated Molecules

• K. Fukui , T. Yonezawa , +1 author H. Shingu
• Published 1 August 1954
• Journal of Chemical Physics

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An orbital interaction rationale for organic molecules and reactions, mo-theoretical approach to the mechanism of charge transfer in the process of aromatic substitutions, perspective on “a molecular orbital theory of reactivity in aromatic hydrocarbons”, the role of the frontier orbitals in acid–base chemistry of organic amines probed by ab initio and chemometric techniques, theoretical study of ionization potentials in monosubstituted benzenes, π electron structure and reactivities of isomeric pyrrolo-sym-triazoles, conformational isomerism of n 2 h 4 and derivatives. the stereochemical consequences of “forbiddenness” removal, theory of substitution in conjugated molecules, quantum chemical study of regioselectivity of reactions of substituted pyrido[1,2-a]benzimidazoles with electrophiles, perspectives on the role of the frontier effective-for-reaction molecular orbital (fermo) in the study of chemical reactivity: an updated review, 6 references, a molecular orbital theory of reactivity in aromatic hydrocarbons, some studies in molecular orbital theory iii. substitution in aromatic and heteroaromatic systems, the electronic structure of conjugated systems ii. unsaturated hydrocarbons and their hetero-derivatives, a correlation between reactivity towards free radicals and free valence number in polycyclic aromatics, a molecular orbital theory of organic chemistry. vi.1 aromatic substitution and addition, free valence in unsaturated hydrocarbons, related papers.

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