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It is essential that mesoscopic simulations of reactive systems reproduce the correct statistical distributions at thermodynamic equilibrium. By considering a compressible fluctuating hydrodynamics (FHD) simulation method of ideal gas mixtures undergoing reversible reactions described by the chemical Langevin equations, we show that thermodynamic consistency in reaction rates and the use of instantaneous temperatures for the evaluation of reaction rates is required for fluctuations for the overall system to be correct. We then formulate the required properties of a thermodynamically consistent reaction (TCR) model. As noted in the literature, while reactions are often discussed in terms of forward and reverse rates, these rates should not be modeled independently because they must be compatible with thermodynamic equilibrium for the system. Using a simple TCR model where each chemical species has constant heat capacity, we derive the explicit condition that the forward and reverse reaction rate constants must satisfy in order for the system to be thermodynamically consistent. We perform equilibrium and non-equilibrium simulations of ideal gas mixtures undergoing a reversible dimerization reaction to measure the fluctuational behavior of the system numerically. We confirm that FHD simulations with the TCR model give the correct static structure factor of equilibrium fluctuations. For the statistically steady simulation of a gas mixture between two isothermal walls with different temperatures, we show using the TCR model that the temperature variance agrees with the corresponding thermodynamic-equilibrium temperature variance in the interior of the system, whereas noticeable deviations are present in regions near walls, where chemistry is far from equilibrium.
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Implementing parallel arithmetic via acetylation and its application to chemical image processing
Chemical mixtures can be leveraged to store large amounts of data in a highly compact form and have the potential for massive scalability owing to the use of large-scale molecular libraries. With the parallelism that comes from having many species available, chemical-based memory can also provide the physical substrate for computation with increased throughput. Here, we represent non-binary matrices in chemical solutions and perform multiple matrix multiplications and additions, in parallel, using chemical reactions. As a case study, we demonstrate image processing, in which small greyscale images are encoded in chemical mixtures and kernel-based convolutions are performed using phenol acetylation reactions. In these experiments, we use the measured concentrations of reaction products (phenyl acetates) to reconstruct the output image. In addition, we establish the chemical criteria required to realize chemical image processing and validate reaction-based multiplication. Most importantly, this work shows that fundamental arithmetic operations can be reliably carried out with chemical reactions. Our approach could serve as a basis for developing more advanced chemical computing architectures.
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- Award ID(s):
- 1941344
- PAR ID:
- 10299347
- Date Published:
- Journal Name:
- Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences
- Volume:
- 477
- Issue:
- 2248
- ISSN:
- 1364-5021
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1098/rspa.2020.0899
