TY - JOUR
T1 - Interconversion-controlled liquid-liquid phase separation in a molecular chiral model
AU - Uralcan, Betul
AU - Longo, Thomas J.
AU - Anisimov, Mikhail A.
AU - Stillinger, Frank H.
AU - Debenedetti, Pablo G.
N1 - Funding Information:
We thank Sergey V. Buldyrev who suggested considering the forced interconversion through an imbalance of intermolecular forces and Nikolai D. Petsev for the development of the code for the conservative-force formulation of the chiral model. M.A.A. and P.G.D. acknowledge the financial support of the National Science Foundation (Award Nos. CHE-1856479 and CHE-1856704, respectively). Simulations were performed on computational resources managed and supported by Princeton Research Computing, a consortium of groups including the Princeton Institute for Computational Science and Engineering (PICSciE) and the Office of Information Technology’s High Performance Computing Center and Visualization Laboratory at Princeton University.
Publisher Copyright:
© 2021 Author(s).
PY - 2021/11/28
Y1 - 2021/11/28
N2 - Liquid-liquid phase separation of fluids exhibiting interconversion between alternative states has been proposed as an underlying mechanism for fluid polyamorphism and may be of relevance to the protein function and intracellular organization. However, molecular-level insight into the interplay between competing forces that can drive or restrict phase separation in interconverting fluids remains elusive. Here, we utilize an off-lattice model of enantiomers with tunable chiral interconversion and interaction properties to elucidate the physics underlying the stabilization and tunability of phase separation in fluids with interconverting states. We show that introducing an imbalance in the intermolecular forces between two enantiomers results in nonequilibrium, arrested phase separation into microdomains. We also find that in the equilibrium case, when all interaction forces are conservative, the growth of the phase domain is restricted only by the system size. In this case, we observe phase amplification, in which one of the two alternative phases grows at the expense of the other. These findings provide novel insights on how the interplay between dynamics and thermodynamics defines the equilibrium and steady-state morphologies of phase transitions in fluids with interconverting molecular or supramolecular states.
AB - Liquid-liquid phase separation of fluids exhibiting interconversion between alternative states has been proposed as an underlying mechanism for fluid polyamorphism and may be of relevance to the protein function and intracellular organization. However, molecular-level insight into the interplay between competing forces that can drive or restrict phase separation in interconverting fluids remains elusive. Here, we utilize an off-lattice model of enantiomers with tunable chiral interconversion and interaction properties to elucidate the physics underlying the stabilization and tunability of phase separation in fluids with interconverting states. We show that introducing an imbalance in the intermolecular forces between two enantiomers results in nonequilibrium, arrested phase separation into microdomains. We also find that in the equilibrium case, when all interaction forces are conservative, the growth of the phase domain is restricted only by the system size. In this case, we observe phase amplification, in which one of the two alternative phases grows at the expense of the other. These findings provide novel insights on how the interplay between dynamics and thermodynamics defines the equilibrium and steady-state morphologies of phase transitions in fluids with interconverting molecular or supramolecular states.
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U2 - 10.1063/5.0071988
DO - 10.1063/5.0071988
M3 - Article
C2 - 34852466
AN - SCOPUS:85120316570
SN - 0021-9606
VL - 155
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 20
M1 - 204502
ER -