Relativistic Linear Response in Quantum-Electrodynamical Density Functional Theory
We present the theoretical derivation and numerical implementation of the linear-response equations for relativistic quantum-electrodynamical density functional theory (QEDFT). In contrast to previous works based on the Pauli-Fierz Hamiltonian, our approach describes electrons interacting with photo...
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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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American Physical Society
2025-08-01
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| Series: | Physical Review X |
| Online Access: | http://doi.org/10.1103/ttc3-867m |
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| _version_ | 1849223274479747072 |
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| author | Lukas Konecny Valeriia P. Kosheleva Heiko Appel Michael Ruggenthaler Angel Rubio |
| author_facet | Lukas Konecny Valeriia P. Kosheleva Heiko Appel Michael Ruggenthaler Angel Rubio |
| author_sort | Lukas Konecny |
| collection | DOAJ |
| description | We present the theoretical derivation and numerical implementation of the linear-response equations for relativistic quantum-electrodynamical density functional theory (QEDFT). In contrast to previous works based on the Pauli-Fierz Hamiltonian, our approach describes electrons interacting with photonic cavity modes at the four-component Dirac-Kohn-Sham level, derived from fully relativistic QED through a series of established approximations. Moreover, we show that a new type of spin-orbit-like (SO) cavity-mediated interaction appears under the relativistic description of the coupling of matter with quantized cavity modes. Benchmark calculations performed for atoms of group 12 elements (Zn, Cd, Hg) demonstrate how a relativistic treatment enables the description of exciton polaritons that arise from the hybridization of formally forbidden singlet-triplet transitions with cavity modes. For atoms in cavities tuned on resonance with a singlet-triplet transition, we discover a significant interplay between SO effects and coupling to an off-resonant intense singlet-singlet transition. This dynamic relationship highlights the crucial role of ab initio approaches in understanding cavity quantum electrodynamics. Finally, using the mercury porphyrin complex as an example, we show that relativistic linear-response QEDFT provides computationally feasible first-principles calculations of polaritonic states in large heavy-element-containing molecules of chemical interest. |
| format | Article |
| id | doaj-art-aeabc9a2f1a74657b9c29a8fc4906f1f |
| institution | Kabale University |
| issn | 2160-3308 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | American Physical Society |
| record_format | Article |
| series | Physical Review X |
| spelling | doaj-art-aeabc9a2f1a74657b9c29a8fc4906f1f2025-08-25T19:03:47ZengAmerican Physical SocietyPhysical Review X2160-33082025-08-0115303105210.1103/ttc3-867mRelativistic Linear Response in Quantum-Electrodynamical Density Functional TheoryLukas KonecnyValeriia P. KoshelevaHeiko AppelMichael RuggenthalerAngel RubioWe present the theoretical derivation and numerical implementation of the linear-response equations for relativistic quantum-electrodynamical density functional theory (QEDFT). In contrast to previous works based on the Pauli-Fierz Hamiltonian, our approach describes electrons interacting with photonic cavity modes at the four-component Dirac-Kohn-Sham level, derived from fully relativistic QED through a series of established approximations. Moreover, we show that a new type of spin-orbit-like (SO) cavity-mediated interaction appears under the relativistic description of the coupling of matter with quantized cavity modes. Benchmark calculations performed for atoms of group 12 elements (Zn, Cd, Hg) demonstrate how a relativistic treatment enables the description of exciton polaritons that arise from the hybridization of formally forbidden singlet-triplet transitions with cavity modes. For atoms in cavities tuned on resonance with a singlet-triplet transition, we discover a significant interplay between SO effects and coupling to an off-resonant intense singlet-singlet transition. This dynamic relationship highlights the crucial role of ab initio approaches in understanding cavity quantum electrodynamics. Finally, using the mercury porphyrin complex as an example, we show that relativistic linear-response QEDFT provides computationally feasible first-principles calculations of polaritonic states in large heavy-element-containing molecules of chemical interest.http://doi.org/10.1103/ttc3-867m |
| spellingShingle | Lukas Konecny Valeriia P. Kosheleva Heiko Appel Michael Ruggenthaler Angel Rubio Relativistic Linear Response in Quantum-Electrodynamical Density Functional Theory Physical Review X |
| title | Relativistic Linear Response in Quantum-Electrodynamical Density Functional Theory |
| title_full | Relativistic Linear Response in Quantum-Electrodynamical Density Functional Theory |
| title_fullStr | Relativistic Linear Response in Quantum-Electrodynamical Density Functional Theory |
| title_full_unstemmed | Relativistic Linear Response in Quantum-Electrodynamical Density Functional Theory |
| title_short | Relativistic Linear Response in Quantum-Electrodynamical Density Functional Theory |
| title_sort | relativistic linear response in quantum electrodynamical density functional theory |
| url | http://doi.org/10.1103/ttc3-867m |
| work_keys_str_mv | AT lukaskonecny relativisticlinearresponseinquantumelectrodynamicaldensityfunctionaltheory AT valeriiapkosheleva relativisticlinearresponseinquantumelectrodynamicaldensityfunctionaltheory AT heikoappel relativisticlinearresponseinquantumelectrodynamicaldensityfunctionaltheory AT michaelruggenthaler relativisticlinearresponseinquantumelectrodynamicaldensityfunctionaltheory AT angelrubio relativisticlinearresponseinquantumelectrodynamicaldensityfunctionaltheory |