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  • Open Access

Correlated dynamics as a resource in molecular switches

Daniel Siciliano*,†, Rudi B. P. Pietsch*,‡, Giovanni Spaventa§, Susana F. Huelga∥, and Martin B. Plenio

  • Institute of Theoretical Physics & IQST, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany

  • *These authors contributed equally to this work.
  • †Contact author: daniel.siciliano@uni-ulm.de
  • ‡Contact author: rudi.pietsch@uni-ulm.de
  • §Contact author: giovanni.spaventa@uni-ulm.de
  • ∥Contact author: susana.huelga@uni-ulm.de
  • Contact author: martin.plenio@uni-ulm.de
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Phys. Rev. A 112, 042411 – Published 6 October, 2025

DOI: https://doi.org/10.1103/khj7-3clh

Abstract

Photoisomerization, a photochemical process underlying many biological mechanisms, has been modeled recently within the quantum resource theory of thermodynamics. This approach has emerged as a promising tool for studying fundamental limitations to nanoscale processes independently of the microscopic details governing their dynamics. On the other hand, correlations between physical systems have been shown to play a crucial role in quantum thermodynamics by lowering the work cost of certain operations. Here we explore quantitatively how correlations between multiple photoswitches can enhance the efficiency of photoisomerization beyond that attainable for single molecules. Furthermore, our analysis provides insights into the interplay between quantum and classical correlations in these transformations.

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References (40)

  1. B. Coecke, T. Fritz, and R. W. Spekkens, A mathematical theory of resources, Inf. Comput. 250, 59 (2016).
  2. E. Chitambar and G. Gour, Quantum resource theories, Rev. Mod. Phys. 91, 025001 (2019).
  3. E. Ruch and A. Mead, The principle of increasing mixing character and some of its consequences, Theor. Chim. Acta 41, 95 (1976).
  4. E. Ruch, R. Schranner, and T. H. Seligman, The mixing distance, J. Chem. Phys. 69, 386 (1978).
  5. D. Janzing, P. Wocjan, R. Zeier, R. Geiss, and T. Beth, Thermodynamic cost of reliability and low temperatures: Tightening Landauer's principle and the second law, Int. J. Theor. Phys. 39, 2717 (2000).
  6. M. Horodecki and J. Oppenheim, Fundamental limitations for quantum and nanoscale thermodynamics, Nat. Commun. 4, 2059 (2013).
  7. J. Goold, M. Huber, A. Riera, L. Del Rio, and P. Skrzypczyk, The role of quantum information in thermodynamics—A topical review, J. Phys. A: Math. Theor. 49, 143001 (2016).
  8. M. Lostaglio, An introductory review of the resource theory approach to thermodynamics, Rep. Prog. Phys. 82, 114001 (2019).
  9. N. H. Y. Ng and M. P. Woods, in Thermodynamics in the Quantum Regime: Fundamental Aspects and New Directions, edited by F. Binder, L. A. Correa, C. Gogolin, J. Anders, and G. Adesso, Fundamental Theories of Physics Vol. 195 (Springer, Berlin, 2018), pp. 625–650.
  10. N. Yunger Halpern and D. T. Limmer, Fundamental limitations on photoisomerization from thermodynamic resource theories, Phys. Rev. A 101, 042116 (2020).
  11. G. Spaventa, S. F. Huelga, and M. B. Plenio, Capacity of non-Markovianity to boost the efficiency of molecular switches, Phys. Rev. A 105, 012420 (2022).
  12. M. Burkhard, O. Pusuluk, and T. Farrow, Boosting biomolecular switch efficiency with quantum coherence, Phys. Rev. A 110, 012411 (2024).
  13. S. Tiwary, G. Spaventa, S. F. Huelga, and M. B. Plenio, Quantum resource-theoretical analysis of the role of vibrational structure in photoisomerization, Phys. Rev. A 112, 032440 (2025).
  14. D. C. Alyürük, M. H. Yeşiller, V. Vedral, and O. Pusuluk, Thermodynamic limits of the mpemba effect: A unified resource theory analysis, arXiv:2502.00123.
  15. We note that some assumptions about the spectrum of the bath are needed (see [6]). However, as the authors discuss, these are naturally satisfied by, e.g., a product τ⊗N of many independent Gibbs states.
  16. T. A. Telegina, Y. L. Vechtomova, A. V. Aybush, A. A. Buglak, and M. S. Kritsky, Isomerization of carotenoids in photosynthesis and metabolic adaptation, Biophys. Rev. 15, 887 (2023).
  17. R. Croce, R. Van Grondelle, H. Van Amerongen, and I. Van Stokkum, Light Harvesting in Photosynthesis (CRC, Boca Raton, 2018).
  18. D. Dattler, G. Fuks, J. Heiser, E. Moulin, A. Perrot, X. Yao, and N. Giuseppone, Design of collective motions from synthetic molecular switches, rotors, and motors, Chem. Rev. 120, 310 (2020).
  19. P. Nogly, T. Weinert, D. James, S. Carbajo, D. Ozerov, A. Furrer, D. Gashi, V. Borin, P. Skopintsev, K. Jaeger et al., Retinal isomerization in bacteriorhodopsin captured by a femtosecond x-ray laser, Science 361, eaat0094 (2018).
  20. L. Seidner and W. Domcke, Microscopic modelling of photoisomerization and internal-conversion dynamics, Chem. Phys. 186, 27 (1994).
  21. L. Seidner, G. Stock, and W. Domcke, Nonperturbative approach to femtosecond spectroscopy: General theory and application to multidimensional nonadiabatic photoisomerization processes, J. Chem. Phys. 103, 3998 (1995).
  22. S. Hahn and G. Stock, Quantum-mechanical modeling of the femtosecond isomerization in rhodopsin, J. Phys. Chem. B 104, 1146 (2000).
  23. S. Hahn and G. Stock, Ultrafast cis-trans photoswitching: A model study, J. Chem. Phys. 116, 1085 (2002).
  24. D. Siciliano, Exploring the role of correlations in boosting the asymptotic efficiency of molecular switches with quantum resource theories, M.Sc. thesis, University of Turin, 2023.
  25. R. B. P. Pietsch, Fundamental limitations to the efficiency of multiple molecular switches from resource theories of thermodynamics, B.Sc. thesis, Ulm University, 2022, available at https://acrobat.adobe.com/id/urn:aaid:sc:VA6C2:b55819d2-ca17-442f-bef3-938d02e51f95.
  26. F. Sapienza, F. Cerisola, and A. J. Roncaglia, Correlations as a resource in quantum thermodynamics, Nat. Commun. 10, 2492 (2019).
  27. D. Jennings and T. Rudolph, Entanglement and the thermodynamic arrow of time, Phys. Rev. E 81, 061130 (2010).
  28. M. H. Partovi, Entanglement versus stosszahlansatz: Disappearance of the thermodynamic arrow in a high-correlation environment, Phys. Rev. E 77, 021110 (2008).
  29. A. M. De Mendoza, F. Caycedo-Soler, S. F. Huelga, and M. B. Plenio, Temporal correlations of sunlight may assist photoprotection in bacterial photosynthesis, New J. Phys. 22, 073042 (2020).
  30. M. Lostaglio, M. P. Müller, and M. Pastena, Stochastic independence as a resource in small-scale thermodynamics, Phys. Rev. Lett. 115, 150402 (2015).
  31. R. Rubboli and M. Tomamichel, Fundamental limits on correlated catalytic state transformations, Phys. Rev. Lett. 129, 120506 (2022).
  32. M. B. Plenio and S. Virmani, An introduction to entanglement measures, Quantum Inf. Comput. 7, 1 (2007).
  33. R. Horodecki, P. Horodecki, M. Horodecki, and K. Horodecki, Quantum entanglement, Rev. Mod. Phys. 81, 865 (2009).
  34. This definition of yield corresponds to the expected number of switched molecules out of the ensemble, which we find to be a natural choice. Other definitions of (two-molecule) yields have been proposed in [12], for example, considering the probability that at least one molecule is found to be switched after the process. However, this choice assigns the same weight to processes switching only one molecule or both, which in principle can have very different thermodynamical costs.
  35. F. G. S. L. Brandão, M. Horodecki, J. Oppenheim, J. M. Renes, and R. W. Spekkens, Resource theory of quantum states out of thermal equilibrium, Phys. Rev. Lett. 111, 250404 (2013).
  36. Z. Wang, P. Erhart, T. Li, Z.-Y. Zhang, D. Sampedro, Z. Hu, H. A. Wegner, O. Brummel, J. Libuda, M. B. Nielsen et al., Storing energy with molecular photoisomers, Joule 5, 3116 (2021).
  37. C. Chuang and P. Brumer, Steady state photoisomerization quantum yield of model rhodopsin: Insights from wavepacket dynamics? J. Phys. Chem. Lett. 13, 4963 (2022).
  38. D. Siciliano, “DanielSic/corr_phot: corr_phot_data (v1.0.0) (2025)” Zenodo, https://doi.org/10.5281/zenodo.17078056.
  39. One should order the energy levels to write down the population vector of the Gibbs state, but that amounts to a permutation which is also applied on the population vector so that the expression for the yield remains the same. An arbitrary order may be assumed.
  40. R. Silva, G. Manzano, P. Skrzypczyk, and N. Brunner, Performance of autonomous quantum thermal machines: Hilbert space dimension as a thermodynamical resource, Phys. Rev. E 94, 032120 (2016).

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Phys. Rev. A 112, 042411– Published 6 October, 2025
  • Received 26 May 2025
  • Accepted 5 September 2025
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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.

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