- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Research

Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Open Access

Quantum-electrodynamical time-dependent density functional theory description of cavity-mediated interactions between spatially separated molecules

Yetmgeta Aklilu1, Tiany Yang1, Cody Covington2, and Kálmán Varga1,*

  • *Contact author: kalman.varga@vanderbilt.edu
PDF

Phys. Rev. Research 8, 023184 – Published 19 May, 2026

DOI: https://doi.org/10.1103/42x4-nlwy

Abstract

We study light-mediated interactions between spatially separated molecules using real-time quantum-electrodynamical time-dependent density functional theory based on the Pauli-Fierz Hamiltonian. An ultrashort delta-kick excitation selectively perturbs a single molecule, while a second, distant molecule remains initially unexcited. In free space, the excitation stays localized and no response is observed in the second molecule. In contrast, when both molecules are coupled to the same cavity mode, the initial excitation induces coherent dynamics in the distant molecule through the shared quantized electromagnetic field.

View figure in article

Physics Subject Headings (PhySH)

Article Text

References (93)

  1. F. J. Garcia-Vidal, C. Ciuti, and T. W. Ebbesen, Manipulating matter by strong coupling to vacuum fields, Science 373, eabd0336 (2021).
  2. M. Ruggenthaler, N. Tancogne-Dejean, J. Flick, H. Appel, and A. Rubio, From a quantum-electrodynamical light–matter description to novel spectroscopies, Nat. Rev. Chem. 2, 0118 (2018).
  3. J. Flick, N. Rivera, and P. Narang, Strong light-matter coupling in quantum chemistry and quantum photonics, Nanophotonics 7, 1479 (2018).
  4. M. Ruggenthaler, D. Sidler, and A. Rubio, Understanding polaritonic chemistry from ab initio quantum electrodynamics, Chem. Rev. 123, 11191 (2023).
  5. D. N. Basov, A. Asenjo-Garcia, P. J. Schuck, X. Zhu, A. Rubio, A. Cavalleri, M. Delor, M. M. Fogler, and M. Liu, Polaritonic quantum matter, Nanophotonics 14, 3723 (2025).
  6. T. W. Ebbesen, Hybrid light–matter states in a molecular and material science perspective, Acc. Chem. Res. 49, 2403 (2016).
  7. J. J. Foley, J. F McTague, and A. E. DePrince, Ab initio methods for polariton chemistry, Chem. Phys. Rev. 4, 041301 (2023).
  8. B. M. Weight, T. D. Krauss, and P. Huo, Investigating molecular exciton polaritons using ab initio cavity quantum electrodynamics, J. Phys. Chem. Lett. 14, 5901 (2023).
  9. N. Bauman, L. A. Cunha, A. Eugene, I. I. I. DePrince, J. Flick, J. J. I. V. Foley, N. Govind, G. Groenhof, N. Hoffmann, K. Kowalski, et al., Perspective on many-body methods for molecular polaritonic systems, J. Chem. Theory Comput. 21, 10035 (2025).
  10. M. Ruggenthaler, J. Flick, C. Pellegrini, H. Appel, I. V. Tokatly, and A. Rubio, Quantum-electrodynamical density-functional theory: Bridging quantum optics and electronic-structure theory, Phys. Rev. A 90, 012508 (2014).
  11. C. Huang, A. Ahrens, M. Beutel, and K. Varga, Two electrons in harmonic confinement coupled to light in a cavity, Phys. Rev. B 104, 165147 (2021).
  12. C. Schafer, F. Buchholz, M. Penz, M. Ruggenthaler, and A. Rubio, Making ab initio QED functional(s): Nonperturbative and photon-free effective frameworks for strong light & matter coupling, Proc. Natl. Acad. Sci. USA 118, e2110464118 (2021).
  13. C. Pellegrini, J. Flick, I. V. Tokatly, H. Appel, and A. Rubio, Optimized effective potential for quantum electrodynamical time-dependent density functional theory, Phys. Rev. Lett. 115, 093001 (2015).
  14. I. V. Tokatly, Time-dependent density functional theory for many-electron systems interacting with cavity photons, Phys. Rev. Lett. 110, 233001 (2013).
  15. M. A. D. Taylor, A. Mandal, W. Zhou, and P. Huo, Resolution of gauge ambiguities in molecular cavity quantum electrodynamics, Phys. Rev. Lett. 125, 123602 (2020).
  16. J. Galego, F. J. Garcia-Vidal, and J. Feist, Cavity-induced modifications of molecular structure in the strong-coupling regime, Phys. Rev. X 5, 041022 (2015).
  17. M. A. D. Taylor, A. Mandal, and P. Huo, Light–matter interaction Hamiltonians in cavity quantum electrodynamics, Chem. Phys. Rev. 6, 011305 (2025).
  18. P. Roden and J. J. Foley, Perturbative analysis of the coherent state transformation in ab initio cavity quantum electrodynamics, J. Chem. Phys. 161, 194103 (2024).
  19. R. Manderna, N. Vu, and J. J. Foley, Comparing parameterized and self-consistent approaches to ab initio cavity quantum electrodynamics for electronic strong coupling, J. Chem. Phys. 161, 174105 (2024).
  20. J. D. Weidman, M. S. Dadgar, Z. J. Stewart, B. G. Peyton, I. S. Ulusoy, and A. K. Wilson, Cavity-modified molecular dipole switching dynamics, J. Chem. Phys. 160, 094111 (2024).
  21. B. M. Weight, X. Li, and Y. Zhang, Theory and modeling of light-matter interactions in chemistry: Current and future, Phys. Chem. Chem. Phys. 25, 31554 (2023).
  22. P. Badankó, O. Umarov, C. Fabri, G. J. Halász, and Á. Vibók, Topological aspects of cavity-induced degeneracies in polyatomic molecules, Int. J. Quantum Chem. 122, e26750 (2022).
  23. G. Mazza and A. Georges, Superradiant quantum materials, Phys. Rev. Lett. 122, 017401 (2019).
  24. O. D. Stefano, A. Settineri, V. Macri, L. Garziano, R. Stassi, S. Savasta, and F. Nori, Resolution of gauge ambiguities in ultrastrong-coupling cavity quantum electrodynamics, Nat. Phys. 15, 803 (2019).
  25. A. Shalabney, J. George, J.  Hutchison, G. Pupillo, C. Genet, and T. W. Ebbesen, Coherent coupling of molecular resonators with a microcavity mode, Nat. Commun. 6, 5981 (2015).
  26. F. Buchholz, I. Theophilou, S. E. B. Nielsen, M. Ruggenthaler, and A. Rubio, Reduced density-matrix approach to strong matter-photon interaction, ACS Photonics 6, 2694 (2019).
  27. C. Schäfer, M. Ruggenthaler, H. Appel, and A. Rubio, Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry, Proc. Natl. Acad. Sci. USA 116, 4883 (2019).
  28. A. E. D. Prince and S. H. Yuwono, Static electric dipole polarizability and hyperpolarizability tensors from mean-field cavity quantum electrodynamics approaches, J. Phys. Chem. A 129, 8024 (2025).
  29. L. Lacombe, N. M. Hoffmann, and N. T. Maitra, Exact potential energysurface for molecules in cavities, Phys. Rev. Lett. 123, 083201 (2019).
  30. A. Mandal, S. M. Vega, and P. Huo, Polarized Fock states and the dynamical Casimir effect in molecular cavity quantum electrodynamics, J. Phys. Chem. Lett. 11, 9215 (2020).
  31. J. Flick, D. M. Welakuh, M. Ruggenthaler, H. Appel, and A. Rubio, Light–matter response in nonrelativistic quantum electrodynamics, ACS Photonics 6, 2757 (2019).
  32. S. Latini, E. Ronca, U. D. Giovannini, H. Hubener, and A. Rubio, Cavity control of excitons in two-dimensional materials, Nano Lett. 19, 3473 (2019).
  33. M. D. Liebenthal, N. Vu, and A. E. DePrince, Assessing the effects of orbital relaxation and the coherent-state transformation in quantum electrodynamics density functional and coupled-cluster theories, J. Phys. Chem. A 127, 5264 (2023).
  34. A. Thomas, L. Lethuillier-Karl, K. Nagarajan, R. M. A. Vergauwe, J. George, T. Chervy, A. Shalabney, E. Devaux, C. Genet, J. Moran, et al., Tilting a ground-state reactivity landscape by vibrational strong coupling, Science 363, 615 (2019).
  35. D. Novokreschenov, A. Kudlis, I. Iorsh, and I. V. Tokatly, Quantum electrodynamical density functional theory for generalized Dicke model, Phys. Rev. B 108, 235424 (2023).
  36. U. Mordovina, C. Bungey, H. Appel, P. J. Knowles, A. Rubio, and F. R. Manby, Polaritonic coupled-cluster theory, Phys. Rev. Res. 2, 023262 (2020).
  37. D. S. Wang, T. Neuman, J. Flick, and P. Narang, Light–matter interaction of a molecule in a dissipative cavity from first principles, J. Chem. Phys. 154, 104109 (2021).
  38. T. S. Haugland, C. Schafer, E. Ronca, A. Rubio, and H. Koch, Intermolecular interactions in optical cavities: An ab initio QED study, J. Chem. Phys. 154, 094113 (2021).
  39. J. Flick and P. Narang, Ab initio polaritonic potential-energy surfaces for excited-state nanophotonics and polaritonic chemistry, J. Chem. Phys. 153, 094116 (2020).
  40. J. Flick, M. Ruggenthaler, H. Appel, and A. Rubio, Kohn–Sham approach to quantum electrodynamical density-functional theory: Exact time-dependent effective potentials in real space, Proc. Natl. Acad. Sci. USA 112, 15285 (2015).
  41. A. Mandal, T. D. Krauss, and P. Huo, Polariton-mediated electron transfer via cavity quantum electrodynamics, J. Phys. Chem. B 124, 6321 (2020).
  42. M. Castagnola, R. R. Riso, A. Barlini, E. Ronca, and H. Koch, Polaritonic response theory for exact and approximate wave functions, WIREs Comput. Mol. Sci. 14, e1684 (2024).
  43. I. V. Tokatly, Conserving approximations in cavity quantum electrodynamics: Implications for density functional theory of electron-photon systems, Phys. Rev. B 98, 235123 (2018).
  44. N. Vu, D. Mejia-Rodriguez, N. P Bauman, A. Panyala, E. Mutlu, N. Govind, and J. J. Foley IV, Cavity quantum electrodynamics complete active space configuration interaction theory, J. Chem. Theory Comput. 20, 1214 (2024).
  45. V. Rokaj, D. M. Welakuh, M. Ruggenthaler, and A. Rubio, Light–matter interaction in the long-wavelength limit: No ground-state without dipole self-energy, J. Phys. B: At. Mol. Opt. Phys. 51, 034005 (2018).
  46. J. Flick, M. Ruggenthaler, H. Appel, and A. Rubio, Atoms and molecules in cavities, from weak to strong coupling in quantum-electrodynamics (QED) chemistry, Proc. Natl. Acad. Sci. USA 114, 3026 (2017).
  47. R. R. Riso, M. Castagnola, E. Ronca, and H. Koch, Chiral polaritonics: Cavity-mediated enantioselective excitation condensation, Rep. Prog. Phys. 88, 027901 (2025).
  48. J.-B. You, J. F. Kong, D. Aghamalyan, W.-K. Mok, K. H. Lim, J. Ye, C. E. Png, and F. J. García-Vidal, Generation and optimization of entanglement between atoms chirally coupled to spin cavities, Phys. Rev. Res. 7, L012058 (2025).
  49. G. S. Agarwal, Control of the Purcell effect via unexcited atoms and exceptional points, Phys. Rev. Res. 6, L012050 (2024).
  50. M. Castagnola, Realistic ab initio predictions of excimer behavior under collective light-matter strong coupling Phys. Rev. X 15, 021040 (2025).
  51. M. F. Welman, T. E. Li, and S. Hammes-Schiffer, Light-matter entanglement in real-time nuclear-electronic orbital polariton dynamics, J. Chem. Theory Comput. 21, 8291 (2025).
  52. J. Feist and F. J Garcia-Vidal, Extraordinary exciton conductance induced by strong coupling, Phys. Rev. Lett. 114, 196402 (2015).
  53. D. M. Coles, N. Somaschi, P. Michetti, C. Clark, P. G. Lagoudakis, P. G. Savvidis, and D. G. Lidzey, Polariton-mediated energy transfer between organic dyes in a strongly coupled optical microcavity, Nat. Mater. 13, 712 (2014).
  54. J. Schachenmayer, C. Genes, E. Tignone, and G. Pupillo, Cavity-enhanced transport of excitons, Phys. Rev. Lett. 114, 196403 (2015).
  55. M. Fierz and W. E. Pauli, On relativistic wave equations for particles of arbitrary spin in an electromagnetic field, Proc. R. Soc. Lond. A 173, 211 (1939).
  56. W. Greiner and J. Reinhardt, Field Quantization (Springer, Berlin, 1996).
  57. D. P. Craig and T. Thirunamachandran, Molecular Quantum Electrodynamics: An Introduction to Radiation-Molecule Interactions (Dover Publishers Mineola, New York, 1998).
  58. T. S. Haugland, E. Ronca, E. F. Kjønstad, A. Rubio, and H. Koch, Coupled cluster theory for molecular polaritons: Changing ground and excited states, Phys. Rev. X 10, 041043 (2020).
  59. R. R. Riso, T. S. Haugland, E. Ronca, and H. Koch, Molecular orbital theory in cavity QED environments, Nat. Commun. 13, 1368 (2022).
  60. M. Bauer and A. Dreuw, Perturbation theoretical approaches to strong light–matter coupling in ground and excited electronic states for the description of molecular polaritons, J. Chem. Phys. 158, 124128 (2023).
  61. M. D. Liebenthal, N. Vu, and A. E. DePrince, III, Equation-of-motion cavity quantum electrodynamics coupled-cluster theory for electron attachment, J. Chem. Phys. 156, 054105 (2022).
  62. N. P. Bauman, H. Pathak, M. D. Liebenthal, A. Panyala, D. Mejia-Rodriguez, N. Govind, and K. Kowalski, Quantum electrodynamics coupled-cluster at scale: High-performance implementation for complex systems, J. Chem. Theory Comput. 22, 294 (2026).
  63. N. Vu, K. Ampoh, M. Matoušek, L. Veis, N. Govind, and J. J. Foley, IV, Modeling strong light-matter coupling in correlated systems: State-averaged cavity quantum electrodynamics complete active space self-consistent field theory, J. Chem. Theory Comput. 21, 8812 (2025).
  64. M. Matoušek, N. Vu, N. Govind, J. J. Foley, IV, and L. Veis, Polaritonic chemistry using the density matrix renormalization group method, J. Chem. Theory Comput. 20, 9424 (2024).
  65. A. Ahrens, C. Huang, M. Beutel, C. Covington, and K. Varga, Stochastic variational approach to small atoms and molecules coupled to quantum field modes in cavity QED, Phys. Rev. Lett. 127, 273601 (2021).
  66. Y. S. Aklilu and K. Varga, Description of the hydrogen atom and the He+ ion in an optical cavity using the Pauli-Fierz Hamiltonian, Phys. Rev. A 110, 043119 (2024).
  67. S. Warren, Y. Wang, C. L. Benavides-Riveros, and D. A. Mazziotti, Quantum algorithm for polaritonic chemistry based on an exact ansatz, Quantum Sci. Technol. 10, 02LT02 (2025).
  68. F. Pavošević and J. Flick, Polaritonic unitary coupled cluster for quantum computations, J. Phys. Chem. Lett. 12, 9100 (2021).
  69. M. Hassan, F. Pavošević, D. S. Wang, and J. Flick, Simulating polaritonic ground states on noisy quantum devices, J. Phys. Chem. Lett. 15, 1373 (2024).
  70. S. Warren, Y. Wang, C. L. Benavides-Riveros, and D. A. Mazziotti, Exact ansatz of fermion-boson systems for a quantum device, Phys. Rev. Lett. 133, 080202 (2024).
  71. Z. Sheng, Y. Ge, J. Chen, W. Li, and Z. Shuai, Quantum computer simulation of molecules in optical cavity, Precis. Chem. 3, 326 (2025).
  72. M. Tudorovskaya and D. Muñoz Ramo, Quantum computing simulation of a mixed spin-boson Hamiltonian and its performance for a cavity quantum electrodynamics problem, Phys. Rev. A 109, 032612 (2024).
  73. E. Chiari, W. Makhlouf, L. Pepe, E. Koridon, J. Klein, B. Senjean, B. Lasorne, and S. Yalouz, Ab initio polaritonic chemistry on diverse quantum computing platforms: Ansatz circuit design for qubit, qudit, and hybrid qubit-qumode architectures, Phys. Rev. A 112, 052433 (2025).
  74. E. Jaynes and F. W. Cummings, Comparison of quantum and semiclassical radiation theories with application to the beam maser, in Proceedings of the IEEE (IEEE, Piscataway, NJ, 1963), Vol. 51, pp. 89–109.
  75. M. A. D. Taylor, A. Mandal, and P. Huo, Resolving ambiguities of the mode truncation in cavity quantum electrodynamics, Opt. Lett. 47, 1446 (2022).
  76. F. Benz, M. K. Schmidt, A. Dreismann, R. Chikkaraddy, Y. Zhang, A. Demetriadou, C. Carnegie, H. Ohadi, B. de Nijs, R. Esteban, J. Aizpurua, and J. J. Baumberg, Single-molecule optomechanics in picocavities, Science 354, 726 (2016).
  77. C. Carnegie, J. Griffiths, B. de Nijs, C. Readman, R. Chikkaraddy, W. M. Deacon, Y. Zhang, I. Szabó, E. Rosta, J. Aizpurua, and J. J. Baumberg, Room-temperature optical picocavities below 1 nm3 accessing single-atom geometries, J. Phys. Chem. Lett. 9, 7146 (2018).
  78. Y. Luo, J. Zhao, A. Fieramosca, Q. Guo, H. Kang, X. Liu, Timothy C. H. Liew, D. Sanvitto, Z. An, S. Ghosh, Z. Wang, H. Xu, and Q. Xiong, Strong light-matter coupling in van der Waals materials, Light Sci. Appl. 13, 203 (2024).
  79. T. Cubaynes, M. R. Delbecq, M. C. Dartiailh, R. Assouly, M. M. Desjardins, L. C. Contamin, L. E. Bruhat, Z. Leghtas, F. Mallet, A. Cottet, and T. Kontos, Highly coherent spin states in carbon nanotubes coupled to cavity photons, npj Quantum Inf. 5, 47 (2019).
  80. S. Blien, P. Steger, N. Hüttner, R. Graaf, and A. K. Hüttel, Quantum capacitance mediated carbon nanotube optomechanics, Nat. Commun. 11, 1636 (2020).
  81. J. Malave, A. Ahrens, D. Pitagora, C. Covington, and K. Varga, Real-space, real-time approach to quantum-electrodynamical time-dependent density functional theory, J. Chem. Phys. 157, 194106 (2022).
  82. Y. Aklilu, M. Shepherd, C. L. Covington, and K. Varga, Quantum-electrodynamical time-dependent density functional theory description of molecules in optical cavities, J. Chem. Theory Comput. 22, 2267 (2026).
  83. M. D. Liebenthal and A. E. DePrince, III, The orientation dependenceof cavity-modified chemistry, J. Chem. Phys. 161, 064109 (2024).
  84. C. Tasci, L. A. Cunha, and J. Flick, Photon many-body dispersion: Exchange-correlation functional for strongly coupled light-matter systems, Phys. Rev. Lett. 134, 073002 (2025).
  85. I. Ahmadabadi, I-T. Lu, L. A. Cunha, M. Ruggenthaler, J. Flick, and A. Rubio, Testing electron-photon exchange-correlation functional performance for many-electron systems under weak and strong light-matter coupling, arXiv:2512.14655.
  86. I-T. Lu, M. Ruggenthaler, N. Tancogne-Dejean, S. Latini, M. Penz, and A. Rubio, Electron-photon exchange-correlation approximation for quantum-electrodynamical density-functional theory, Phys. Rev. A 109, 052823 (2024).
  87. D. Mejia-Rodriguez and N. Govind, A meta-generalized gradient approximation for the cavity-dependent exchange-correlation interaction in strongly coupled light–matter systems, J. Phys. Chem. Lett. 16, 13139 (2025).
  88. K. Yabana and G. F. Bertsch, Time-dependent local-density approximation in real time, Phys. Rev. B 54, 4484 (1996).
  89. M. A. L. Marques, A. Castro, G. F. Bertsch, and A. Rubio, Octopus: A first-principles tool for excited electron–ion dynamics, Comput. Phys. Commun. 151, 60 (2003).
  90. K. Varga and J. Driscoll, Computational Nanoscience: Applications for Molecules, Clusters, and Solids (Cambridge University Press, Cambridge, 2011).
  91. N. Troullier and J. Martins, Efficient pseudopotentials for plane-wave calculations, Phys. Rev. B 43, 1993 (1991).
  92. J. P. Perdew, K. Burke, and Y. Wang, Generalized gradient approximation for the exchange-correlation hole of a many-electron system, Phys. Rev. B 54, 16533 (1996).
  93. M. R. Fiechter and M. K. Svendsen, On the Hamiltonian used in polaritonic chemistry, arXiv:2509.15919.

Outline

Information

Phys. Rev. Research 8, 023184– Published 19 May, 2026
  • Received 20 January 2026
  • Accepted 6 May 2026
Crossmark - Check for updates button
Creative Commons Logo

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation