- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Letters

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

Two-Dimensional Electronic Spectroscopy with Intense Entangled-Photon Beams

Deependra Jadoun1,2,*, Upendra Harbola3, Vladimir Y. Chernyak4,5, and Shaul Mukamel2,6,†

  • *Contact author: deependra.jadoun@chemphys.lu.se
  • †Contact author: smukamel@uci.edu
PDF

Phys. Rev. Lett. 135, 223803 – Published 25 November, 2025

DOI: https://doi.org/10.1103/bscm-ndnk

Abstract

Entangled photons carry nontrivial quantum correlations that defy classical physics and provide new tools for monitoring quantum dynamics in molecules. The use of low-flux entangled photons in molecular spectroscopy has been proposed in the past to probe excited-state dynamics with enhanced temporal and spectral resolutions. However, these techniques have been challenging to implement experimentally since the resulting signal has a low signal-to-noise ratio. The signal strength can be boosted by using intense entangled-photon beams, where multiple pairs of entangled photons are present in the environment. This allows the molecule under study to interact with both entangled and unentangled photons, where the classical component of the spectroscopic signal stemming from the latter can mask the spectral features associated with the former. In this Letter, we show how the signal arising from unentangled photons can be eliminated when intense entangled-photon beams are used in two-dimensional electronic spectroscopy (2DES), and demonstrate the advantage of photonic entanglement.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (55)

  1. V. Vedral, Quantum entanglement, Nat. Phys. 10, 256 (2014).
  2. R. Horodecki, P. Horodecki, M. Horodecki, and K. Horodecki, Quantum entanglement, Rev. Mod. Phys. 81, 865 (2009).
  3. M. Erhard, M. Krenn, and A. Zeilinger, Advances in high-dimensional quantum entanglement, Nat. Rev. Phys. 2, 365 (2020).
  4. Y. Shih, Entangled photons, IEEE J. Sel. Top. Quantum Electron. 9, 1455 (2003).
  5. A. Eshun, O. Varnavski, J. P. Villabona-Monsalve, R. K. Burdick, and T. Goodson III, Entangled photon spectroscopy, Accounts Chem. Res. 55, 991 (2022).
  6. S. Szoke, H. Liu, B. P. Hickam, M. He, and S. K. Cushing, Entangled light–matter interactions and spectroscopy, J. Mater. Chem. C 8, 10732 (2020).
  7. D.-I. Lee and T. Goodson, Entangled photon absorption in an organic porphyrin dendrimer, J. Phys. Chem. B 110, 25582 (2006).
  8. L. Moretti, E. Rojas-Gatjens, L. Uboldi, D. O. Tiede, E. J. Kumar, C. Trovatello, F. Preda, A. Perri, C. Manzoni, G. Cerullo et al., Measurement principles for quantum spectroscopy of molecular materials with entangled photons, J. Chem. Phys. 159, 084201 (2023).
  9. A. Ishizaki, Probing excited-state dynamics with quantum entangled photons: Correspondence to coherent multidimensional spectroscopy, J. Chem. Phys. 153, 051102 (2020).
  10. J. Javanainen and P. L. Gould, Linear intensity dependence of a two-photon transition rate, Phys. Rev. A 41, 5088 (1990).
  11. K. E. Dorfman, F. Schlawin, and S. Mukamel, Nonlinear optical signals and spectroscopy with quantum light, Rev. Mod. Phys. 88, 045008 (2016).
  12. M. G. Raymer, T. Landes, and A. H. Marcus, Entangled two-photon absorption by atoms and molecules: A quantum optics tutorial, J. Chem. Phys. 155, 081501 (2021).
  13. F. Schlawin, K. E. Dorfman, and S. Mukamel, Entangled two-photon absorption spectroscopy, Accounts Chem. Res. 51, 2207 (2018).
  14. M. G. Raymer, A. H. Marcus, J. R. Widom, and D. L. Vitullo, Entangled photon-pair two-dimensional fluorescence spectroscopy (EPP-2DFS), J. Phys. Chem. B 117, 15559 (2013).
  15. B. Gu, S. Sun, F. Chen, and S. Mukamel, Photoelectron spectroscopy with entangled photons; enhanced spectrotemporal resolution, Proc. Natl. Acad. Sci. U.S.A. 120, e2300541120 (2023).
  16. S. T. Cundiff and S. Mukamel, Optical multidimensional coherent spectroscopy, Phys. Today 66, No. 7, 44 (2013).
  17. P. Hamm and M. Zanni, Concepts and Methods of 2D Infrared Spectroscopy (Cambridge University Press, Cambridge, United Kingdom, 2011).
  18. H. Li, B. Lomsadze, G. Moody, C. Smallwood, and S. Cundiff, Optical Multidimensional Coherent Spectroscopy (Oxford University Press, New York, 2023).
  19. F. Schlawin, Entangled photon spectroscopy, J. Phys. B 50, 203001 (2017).
  20. S. Mukamel, M. Freyberger, W. Schleich, M. Bellini, A. Zavatta, G. Leuchs, C. Silberhorn, R. W. Boyd, L. L. Sánchez-Soto, A. Stefanov et al., Roadmap on quantum light spectroscopy, J. Phys. B 53, 072002 (2020).
  21. J. J. Fan, Z.-Y. Ou, and Z. Zhang, Entangled photons enabled ultrafast stimulated Raman spectroscopy for molecular dynamics, Light 13, 163 (2024).
  22. K. E. Dorfman, S. Asban, B. Gu, and S. Mukamel, Hong-ou-mandel interferometry and spectroscopy using entangled photons, Commun. Phys. 4, 49 (2021).
  23. T. Landes, M. G. Raymer, M. Allgaier, S. Merkouche, B. J. Smith, and A. H. Marcus, Quantifying the enhancement of two-photon absorption due to spectral-temporal entanglement, Opt. Express 29, 20022 (2021).
  24. M. Kizmann, H. K. Yadalam, V. Y. Chernyak, and S. Mukamel, Quantum interferometry and pathway selectivity in the nonlinear response of photosynthetic excitons, Proc. Natl. Acad. Sci. U.S.A. 120, e2304737120 (2023).
  25. H. K. Yadalam, M. Kizmann, J. R. Rouxel, Y. Nam, V. Y. Chernyak, and S. Mukamel, Quantum interferometric pathway selectivity in difference-frequency-generation spectroscopy, J. Phys. Chem. Lett. 14, 10803 (2023).
  26. Y. Fujihashi, A. Ishizaki, and R. Shimizu, Pathway selectivity in time-resolved spectroscopy using two-photon coincidence counting with quantum entangled photons, J. Chem. Phys. 160, 104201 (2024).
  27. S. Asban and S. Mukamel, Distinguishability and “which pathway” information in multidimensional interferometric spectroscopy with a single entangled photon-pair, Sci. Adv. 7, eabj4566 (2021).
  28. D. Jadoun, H. K. Yadalam, U. Harbola, V. Y. Chernyak, M. Kizmann, and S. Mukamel, Pathway selectivity in 2D electronic-vibrational spectroscopy with quantum light, Laser Photonics Rev. 19, 2401576 (2025).
  29. F. Chen, B. Gu, and S. Mukamel, Monitoring wavepacket dynamics at conical intersections by entangled two-photon absorption, ACS Photonics 9, 1889 (2022).
  30. D. Jadoun, Z. Zhang, and M. Kowalewski, Raman spectroscopy of conical intersections using entangled photons, J. Phys. Chem. Lett. 15, 2023 (2024).
  31. T. Landes, B. J. Smith, and M. G. Raymer, Limitations in fluorescence-detected entangled two-photon-absorption experiments: Exploring the low-to high-gain squeezing regimes, Phys. Rev. A 110, 033708 (2024).
  32. F. Presutti, L. G. Wright, S.-Y. Ma, T. Wang, B. K. Malia, T. Onodera, and P. L. McMahon, Highly multimode visible squeezed light with programmable spectral correlations through broadband up-conversion, arXiv:2401.06119.
  33. B. Dayan, Theory of two-photon interactions with broadband down-converted light and entangled photons, Phys. Rev. A 76, 043813 (2007).
  34. F. Schlawin and S. Mukamel, Photon statistics of intense entangled photon pulses, J. Phys. B 46, 175502 (2013).
  35. J. D. Hybl, A. W. Albrecht, S. M. G. Faeder, and D. M. Jonas, Two-dimensional electronic spectroscopy, Chem. Phys. Lett. 297, 307 (1998).
  36. E. Fresch, F. V. Camargo, Q. Shen, C. C. Bellora, T. Pullerits, G. S. Engel, G. Cerullo, and E. Collini, Two-dimensional electronic spectroscopy, Nat. Rev. Methods Primers 3, 84 (2023).
  37. D. Jadoun, U. Harbola, V. Y. Chernyak, and S. Mukamel, Pump-intensity-scaling of two-photon-absorption and photon statistics of entangled-photon fields, J. Phys. Chem. Lett. 16, 4547 (2025).
  38. A. A. Bakulin, S. E. Morgan, T. B. Kehoe, M. W. Wilson, A. W. Chin, D. Zigmantas, D. Egorova, and A. Rao, Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy, Nat. Chem. 8, 16 (2016).
  39. N. S. Ginsberg, Y.-C. Cheng, and G. R. Fleming, Two-dimensional electronic spectroscopy of molecular aggregates, Accounts Chem. Res. 42, 1352 (2009).
  40. F. Milota, J. Sperling, A. Nemeth, T. Mancal, and H. F. Kauffmann, Two-dimensional electronic spectroscopy of molecular excitons, Accounts Chem. Res. 42, 1364 (2009).
  41. J. Krumland, M. Guerrini, A. De Sio, C. Lienau, and C. Cocchi, Two-dimensional electronic spectroscopy from first principles, Appl. Phys. Rev. 11, 011305 (2024).
  42. M. Cho, H. M. Vaswani, T. Brixner, J. Stenger, and G. R. Fleming, Exciton analysis in 2D electronic spectroscopy, J. Phys. Chem. B 109, 10542 (2005).
  43. S. Biswas, J. Kim, X. Zhang, and G. D. Scholes, Coherent two-dimensional and broadband electronic spectroscopies, Chem. Rev. 122, 4257 (2022).
  44. E. L. Read, G. S. Engel, T. R. Calhoun, T. Mančal, T. K. Ahn, R. E. Blankenship, and G. R. Fleming, Cross-peak-specific two-dimensional electronic spectroscopy, Proc. Natl. Acad. Sci. U.S.A. 104, 14203 (2007).
  45. D. Zigmantas, E. L. Read, T. Mančal, T. Brixner, A. T. Gardiner, R. J. Cogdell, and G. R. Fleming, Two-dimensional electronic spectroscopy of the B800–B820 light-harvesting complex, Proc. Natl. Acad. Sci. U.S.A. 103, 12672 (2006).
  46. E. Brambilla, A. Gatti, M. Bache, and L. A. Lugiato, Simultaneous near-field and far-field spatial quantum correlations in the high-gain regime of parametric down-conversion, Phys. Rev. A 69, 023802 (2004).
  47. A. Christ, B. Brecht, W. Mauerer, and C. Silberhorn, Theory of quantum frequency conversion and type-II parametric down-conversion in the high-gain regime, New J. Phys. 15, 053038 (2013).
  48. H. Defienne, W. P. Bowen, M. Chekhova, G. B. Lemos, D. Oron, S. Ramelow, N. Treps, and D. Faccio, Advances in quantum imaging, Nat. Photonics 18, 1024 (2024).
  49. R. J. Glauber, The quantum theory of optical coherence, Phys. Rev. 130, 2529 (1963).
  50. C. A. Marx, U. Harbola, and S. Mukamel, Nonlinear optical spectroscopy of single, few, and many molecules: Nonequilibrium green’s function QED approach, Phys. Rev. A 77, 022110 (2008).
  51. S. Mukamel, Principles of Nonlinear Optical Spectroscopy (Oxford University Press, New York, 1995).
  52. K. Y. Spasibko, T. S. Iskhakov, and M. V. Chekhova, Spectral properties of high-gain parametric down-conversion, Opt. Express 20, 7507 (2012).
  53. See Supplemental Material at http://link.aps.org/supplemental/10.1103/bscm-ndnk for the signal derivation, nonperturbative treatment of the PDC process, additional spectra, and Feynman diagrams.
  54. L. Ko, R. L. Cook, and K. B. Whaley, Emulating quantum entangled biphoton spectroscopy using classical light pulses, J. Phys. Chem. Lett. 14, 8050 (2023).
  55. D. Jadoun, U. Harbola, V. Chernyak, and S. Mukamel, Two-dimensional electronic spectroscopy with intense entangled-photon beams, 10.5281/zenodo.17348574 (2025).

Outline

Information

Phys. Rev. Lett. 135, 223803– Published 25 November, 2025
  • Received 18 April 2025
  • Revised 14 October 2025
  • Accepted 3 November 2025
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. Funded by Bibsam.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation