TY - JOUR
T1 - Kinetic model for the chiral symmetry breaking transition in the growth front of a conglomerate crystal phase
AU - Asakura, Kouichi
AU - Nagasaka, Yasushi
AU - Osanai, Shuichi
AU - Kondepudi, Dilip K.
PY - 2005/2/3
Y1 - 2005/2/3
N2 - In its molten phase, 1,1′-binaphthyl is racemic due to its high racemization rate, but it can crystallize as a conglomerate of R and S crystals. Our experiments have indicated that, under some conditions, the crystal growth front of 1,1′-binaphthyl shows many of the characteristics of an open system in which chiral symmetry is broken; i.e., the growing solid phase becomes predominantly R or S. Here we present a kinetic model to explain the observed chiral symmetry breaking. The model is based on growth due to attachment of R or S growth units to a crystal surface in a supercooled melt, Chiral symmetry breaking occurs due to chirally autocatalytic formation of R or S growth units on the growth surface. Unlike the many models suggested and studied in the 1980s, there is no cross-inhibition between R- and S-enantiomer in the model presented here. In our model, asymmetric and symmetric steady-state solutions that do not intersect were found. Through linear stability analysis, the critical point, at which a symmetric solution becomes unstable and makes a transition to an asymmetric solution, is determined.
AB - In its molten phase, 1,1′-binaphthyl is racemic due to its high racemization rate, but it can crystallize as a conglomerate of R and S crystals. Our experiments have indicated that, under some conditions, the crystal growth front of 1,1′-binaphthyl shows many of the characteristics of an open system in which chiral symmetry is broken; i.e., the growing solid phase becomes predominantly R or S. Here we present a kinetic model to explain the observed chiral symmetry breaking. The model is based on growth due to attachment of R or S growth units to a crystal surface in a supercooled melt, Chiral symmetry breaking occurs due to chirally autocatalytic formation of R or S growth units on the growth surface. Unlike the many models suggested and studied in the 1980s, there is no cross-inhibition between R- and S-enantiomer in the model presented here. In our model, asymmetric and symmetric steady-state solutions that do not intersect were found. Through linear stability analysis, the critical point, at which a symmetric solution becomes unstable and makes a transition to an asymmetric solution, is determined.
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U2 - 10.1021/jp0470041
DO - 10.1021/jp0470041
M3 - Article
C2 - 16851129
AN - SCOPUS:13444260908
SN - 1520-6106
VL - 109
SP - 1586
EP - 1592
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 4
ER -