Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems

We consider the sensitivity of chemical reactions, able to undergo spontaneous mirror symmetry breaking, to chiral bias in the presence of nonequilibrium temperature fluctuations and derive a selectivity criterion. For this, we estimate the magnitude of fluctuations δk in chemical reaction rate cons...

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Main Authors: David Hochberg, Thomas Buhse, Jean-Claude Micheau, Josep M. Ribó
Format: Article
Language:English
Published: American Physical Society 2022-09-01
Series:Physical Review Research
Online Access:http://doi.org/10.1103/PhysRevResearch.4.033183
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author David Hochberg
Thomas Buhse
Jean-Claude Micheau
Josep M. Ribó
author_facet David Hochberg
Thomas Buhse
Jean-Claude Micheau
Josep M. Ribó
author_sort David Hochberg
collection DOAJ
description We consider the sensitivity of chemical reactions, able to undergo spontaneous mirror symmetry breaking, to chiral bias in the presence of nonequilibrium temperature fluctuations and derive a selectivity criterion. For this, we estimate the magnitude of fluctuations δk in chemical reaction rate constants k arising from the nonequilibrium temperature fluctuations δT about a mean value T. To leading order, the relative rate constant fluctuations δk_{i}/k_{i} for each reaction i are given by the product of the activation enthalpy ΔH_{i}^{‡}/RT for the ith reaction multiplied by the relative rms temperature fluctuations δT_{rms}/T. The latter are determined by the system's specific heat at constant volume: C_{V}. We test this criterion with simulations carried out for an open-flow fully reversible Frank model, and for a range of parity-violating energy differences (PVED) within the theoretically estimated upper and lower bounds. Depending on the relative magnitudes of the deterministic PVED bias and the temperature fluctuations, the PVED bias can either (i) select the final stable chiral outcome deterministically or (ii) select one of two possible stable chiral outcomes with an asymmetric statistical weighting. For larger temperature fluctuations, the PVED bias loses its selectivity, and the final stable chiral outcomes are stochastic and equally probable. This paper points towards the possible design of small volume chemical flow reactors capable of detecting the elusive PVED bias in bulk systems, provided other sources of fluctuations can be sufficiently controlled and attenuated.
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spelling doaj.art-33c390759a1d4ec3b7c2f353c05337bf2024-04-12T17:24:17ZengAmerican Physical SocietyPhysical Review Research2643-15642022-09-014303318310.1103/PhysRevResearch.4.033183Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systemsDavid HochbergThomas BuhseJean-Claude MicheauJosep M. RibóWe consider the sensitivity of chemical reactions, able to undergo spontaneous mirror symmetry breaking, to chiral bias in the presence of nonequilibrium temperature fluctuations and derive a selectivity criterion. For this, we estimate the magnitude of fluctuations δk in chemical reaction rate constants k arising from the nonequilibrium temperature fluctuations δT about a mean value T. To leading order, the relative rate constant fluctuations δk_{i}/k_{i} for each reaction i are given by the product of the activation enthalpy ΔH_{i}^{‡}/RT for the ith reaction multiplied by the relative rms temperature fluctuations δT_{rms}/T. The latter are determined by the system's specific heat at constant volume: C_{V}. We test this criterion with simulations carried out for an open-flow fully reversible Frank model, and for a range of parity-violating energy differences (PVED) within the theoretically estimated upper and lower bounds. Depending on the relative magnitudes of the deterministic PVED bias and the temperature fluctuations, the PVED bias can either (i) select the final stable chiral outcome deterministically or (ii) select one of two possible stable chiral outcomes with an asymmetric statistical weighting. For larger temperature fluctuations, the PVED bias loses its selectivity, and the final stable chiral outcomes are stochastic and equally probable. This paper points towards the possible design of small volume chemical flow reactors capable of detecting the elusive PVED bias in bulk systems, provided other sources of fluctuations can be sufficiently controlled and attenuated.http://doi.org/10.1103/PhysRevResearch.4.033183
spellingShingle David Hochberg
Thomas Buhse
Jean-Claude Micheau
Josep M. Ribó
Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems
Physical Review Research
title Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems
title_full Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems
title_fullStr Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems
title_full_unstemmed Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems
title_short Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems
title_sort resilience of parity violation induced chiral selectivity to nonequilibrium temperature fluctuations in open systems
url http://doi.org/10.1103/PhysRevResearch.4.033183
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AT jeanclaudemicheau resilienceofparityviolationinducedchiralselectivitytononequilibriumtemperaturefluctuationsinopensystems
AT josepmribo resilienceofparityviolationinducedchiralselectivitytononequilibriumtemperaturefluctuationsinopensystems