TY - JOUR
T1 - Fluid-fluid phase transitions in a chiral molecular model
AU - Wang, Yiming
AU - Stillinger, Frank H.
AU - Debenedetti, Pablo G.
N1 - Funding Information:
P.G.D. acknowledges the support of the National Science Foundation (Award No. CHE-1856704). 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. We thank Nikolai Petsev, Betul Uralcan, and Folarin Latinwo for helpful discussions.
Publisher Copyright:
© 2022 Author(s).
PY - 2022/8/28
Y1 - 2022/8/28
N2 - Molecular chirality is a fundamental phenomenon, underlying both life as we know it and industrial pharmaceutical syntheses. Understanding the symmetry breaking phase transitions exhibited by many chiral molecular substances provides basic insights for topics ranging from the origin of life to the rational design of drug manufacturing processes. In this work, we have performed molecular dynamics simulations to investigate the fluid-fluid phase transitions of a flexible three-dimensional four-site chiral molecular model developed by Latinwo et al. [J. Chem. Phys. 145, 154503 (2016)] and Petsev et al. [J. Chem. Phys. 155, 084105 (2021)]. By introducing a bias favoring local homochiral vs heterochiral interactions, the system exhibits a phase transition from a single achiral phase to a single chiral phase that undergoes infrequent interconversion between the two thermodynamically identical chiral states: the L-rich and D-rich phases. According to the phase rule, this reactive binary system has two independent degrees of freedom and exhibits a density-dependent critical locus. Below the liquid-liquid critical locus, there exists a first-order vapor-liquid coexistence region with a single independent degree of freedom. Our results provide basic thermodynamic and kinetic insights for understanding many-body chiral symmetry breaking phenomena.
AB - Molecular chirality is a fundamental phenomenon, underlying both life as we know it and industrial pharmaceutical syntheses. Understanding the symmetry breaking phase transitions exhibited by many chiral molecular substances provides basic insights for topics ranging from the origin of life to the rational design of drug manufacturing processes. In this work, we have performed molecular dynamics simulations to investigate the fluid-fluid phase transitions of a flexible three-dimensional four-site chiral molecular model developed by Latinwo et al. [J. Chem. Phys. 145, 154503 (2016)] and Petsev et al. [J. Chem. Phys. 155, 084105 (2021)]. By introducing a bias favoring local homochiral vs heterochiral interactions, the system exhibits a phase transition from a single achiral phase to a single chiral phase that undergoes infrequent interconversion between the two thermodynamically identical chiral states: the L-rich and D-rich phases. According to the phase rule, this reactive binary system has two independent degrees of freedom and exhibits a density-dependent critical locus. Below the liquid-liquid critical locus, there exists a first-order vapor-liquid coexistence region with a single independent degree of freedom. Our results provide basic thermodynamic and kinetic insights for understanding many-body chiral symmetry breaking phenomena.
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U2 - 10.1063/5.0105851
DO - 10.1063/5.0105851
M3 - Article
C2 - 36049994
AN - SCOPUS:85137091851
SN - 0021-9606
VL - 157
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 8
M1 - 084501
ER -