Transformation-free generation of a quasi-diabatic representation from the state-average orbital-optimized variational quantum eigensolver
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arXiv
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| Autori principali: | , , , , |
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| Natura: | Preprint |
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2025
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| _version_ | 1866908677950144512 |
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| author | Illésová, Silvie Beseda, Martin Yalouz, Saad Lasorne, Benjamin Senjean, Bruno |
| author_facet | Illésová, Silvie Beseda, Martin Yalouz, Saad Lasorne, Benjamin Senjean, Bruno |
| contents | In the present work, we examine how the recent quantum-computing algorithm known as the state-average orbital-optimized variational quantum eigensolver (SA-OO-VQE), viewed within the context of quantum chemistry as a type of multiconfiguration self-consistent field (MCSCF) electronic-structure approach, exhibits a propensity to produce an ab initio quasi-diabatic representation ``for free'' if considered as a least-transformed block-diagonalization procedure, as alluded to in our previous work [S. Yalouz et al., J. Chem. Theory Comput. 18 (2022) 776] and thoroughly assessed herein. To this end, we introduce intrinsic and residual descriptors of diabaticity and re-explore the definition and linear-algebra properties - as well as their consequences on the vibronic nonadiabatic couplings - of an optimal diabatic representation within this context, and how much one may deviate from it. Such considerations are illustrated numerically on the prototypical case of formaldimine, which presents a well-known conical intersection between its ground and first-excited singlet electronic states. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2502_18194 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Transformation-free generation of a quasi-diabatic representation from the state-average orbital-optimized variational quantum eigensolver Illésová, Silvie Beseda, Martin Yalouz, Saad Lasorne, Benjamin Senjean, Bruno Chemical Physics Quantum Physics In the present work, we examine how the recent quantum-computing algorithm known as the state-average orbital-optimized variational quantum eigensolver (SA-OO-VQE), viewed within the context of quantum chemistry as a type of multiconfiguration self-consistent field (MCSCF) electronic-structure approach, exhibits a propensity to produce an ab initio quasi-diabatic representation ``for free'' if considered as a least-transformed block-diagonalization procedure, as alluded to in our previous work [S. Yalouz et al., J. Chem. Theory Comput. 18 (2022) 776] and thoroughly assessed herein. To this end, we introduce intrinsic and residual descriptors of diabaticity and re-explore the definition and linear-algebra properties - as well as their consequences on the vibronic nonadiabatic couplings - of an optimal diabatic representation within this context, and how much one may deviate from it. Such considerations are illustrated numerically on the prototypical case of formaldimine, which presents a well-known conical intersection between its ground and first-excited singlet electronic states. |
| title | Transformation-free generation of a quasi-diabatic representation from the state-average orbital-optimized variational quantum eigensolver |
| topic | Chemical Physics Quantum Physics |
| url | https://arxiv.org/abs/2502.18194 |