Comparing parameterized and self-consistent approaches to ab inito CQED for electronic strong coupling DOI Creative Commons
Ruby Manderna, Nam T. Vu, Jonathan J. Foley

et al.

Published: June 6, 2024

Molecules under strong or ultra-strong light-matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter photon degrees freedom on equal quantum mechanical footing. In the regime molecular electronic one a few molecules, it is desirable treat using tools ab initio chemistry, yielding approach referred as cavity electrodynamics (ai-QED), where are treated at level electrodynamics. this letter, we analyze two complementary approaches ai-QED: (1) parameterized CQED (pQED), two-step computed existing structure theories, enabling construction ai-QED Hamiltonians in basis many-electron eigenstates, (2) self-consistent (scQED), one-step methods generalized include between freedom. Although these equivalent their exact limits, identify disparity projection two-body dipole self-energy operator that appears pQED its counterpart scQED approach. We provide argument resolves only limit complete orbital for projection. numerical results highlighting resolution simple systems, possible limits simultaneously. Additionally, examine compare practical issue computational cost required converge each towards bases.

Language: Английский

Comparing parameterized and self-consistent approaches to ab inito CQED for electronic strong coupling DOI Creative Commons
Ruby Manderna, Nam T. Vu, Jonathan J. Foley

et al.

Published: June 6, 2024

Molecules under strong or ultra-strong light-matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter photon degrees freedom on equal quantum mechanical footing. In the regime molecular electronic one a few molecules, it is desirable treat using tools ab initio chemistry, yielding approach referred as cavity electrodynamics (ai-QED), where are treated at level electrodynamics. this letter, we analyze two complementary approaches ai-QED: (1) parameterized CQED (pQED), two-step computed existing structure theories, enabling construction ai-QED Hamiltonians in basis many-electron eigenstates, (2) self-consistent (scQED), one-step methods generalized include between freedom. Although these equivalent their exact limits, identify disparity projection two-body dipole self-energy operator that appears pQED its counterpart scQED approach. We provide argument resolves only limit complete orbital for projection. numerical results highlighting resolution simple systems, possible limits simultaneously. Additionally, examine compare practical issue computational cost required converge each towards bases.

Language: Английский

Citations

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