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Fundamental limitations on photoisomerization from thermodynamic resource theories

Yunger Halpern, Nicole and Limmer, David T. (2018) Fundamental limitations on photoisomerization from thermodynamic resource theories. . (Submitted)

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Small, out-of-equilibrium, and quantum systems defy simple thermodynamic expressions. Such systems are exemplified by molecular switches, which exchange heat with a bath and which can photoisomerize, or change conformation upon absorbing light. The likelihood of photoisomerization depends on kinetic details that couple the molecule's internal energetics with its interaction with the bath, hindering predictions. We derive simple, general bounds on the photoisomerization yield, using a resource-theory model for thermodynamics. The resource-theory framework is a set of mathematical tools, developed in quantum information theory, for modeling any setting in which constraints restrict the operations performable and the systems accessible. Resource theories are being used to generalize thermodynamics to small and quantum settings. Specifically, we use the thermomajorization preorder, a resource-theory generalization of the second law. Thermomajorization follows from the minimal assumptions of energy conservation and a fixed bath temperature. Using thermomajorization, we upper-bound the photoisomerization yield. Then, we compare the bound with expectations from detailed balance and from simple Lindbladian evolution. Our minimal assumptions constrain the yield tightly if a laser barely excites the molecule, such that thermal fluctuations drive conformation changes, and weakly if the laser excites the molecule to one high-energy eigenstate. We also quantify and bound the coherence in the molecule's post-photoisomerization electronic state. Electronic coherence cannot boost the yield in the absence of extra resources, we argue, because modes of coherence transform independently via resource-theory operations. This work illustrates how thermodynamic resource theories can offer insights into complex quantum processes in nature, experiments, and synthetics.

Item Type:Report or Paper (Discussion Paper)
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URLURL TypeDescription Paper
Yunger Halpern, Nicole0000-0001-8670-6212
Additional Information:NYH thanks Bassam Helou, David Jennings, Christopher Perry, and Mischa Woods for conversations. NYH is grateful for funding from the Institute for Quantum Information and Matter, an NSF Physics Frontiers Center (NSF Grant PHY-1125565) with support from the Gordon and Betty Moore Foundation (GBMF-2644), for a Barbara Groce Graduate Fellowship, for a KITP Graduate Fellowship (the KITP receives support from the NSF under Grant No. NSF PHY-1125915), and for an NSF grant for the Institute for Theoretical Atomic, Molecular, and Optical Physics at Harvard University and the Smithsonian Astrophysical Observatory. DTL was supported by UC Berkeley College of Chemistry and by the Kavli Energy NanoSciences Institute.
Group:IQIM, Institute for Quantum Information and Matter
Funding AgencyGrant Number
NSF Physics Frontiers CenterPHY-1125565
Gordon and Betty Moore FoundationGBMF-2644
Barbara Groce Graduate Fellowship, CaltechUNSPECIFIED
Institute for Theoretical Atomic, Molecular,and Optical Physics at Harvard UniversityUNSPECIFIED
Smithsonian Astrophysical ObservatoryUNSPECIFIED
University of California, BerkeleyUNSPECIFIED
Kavli Energy NanoSciences InstituteUNSPECIFIED
Record Number:CaltechAUTHORS:20190207-150038978
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:92769
Deposited By: Bonnie Leung
Deposited On:15 Feb 2019 21:01
Last Modified:17 Feb 2019 13:53

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