Triplet correlations dominate the transition from simple to tetrahedral liquids.
The total, triplet, and pair contributions to the entropy with increasing tetrahedrality are mapped out for the Stillinger-Weber liquids to demonstrate the qualitative and quantitative differences between triplet-dominated, tetrahedral liquids and pair-dominated, simple liquids with regard to supercooling and crystallization. The heat capacity anomaly of tetrahedral liquids originates in local ordering due to both pair and triplet correlations. The results suggest that structural correlations can be directly related to thermodynamic anomalies, phase changes, and self-assembly in other atomic and colloidal fluids.
School of Physical Sciences, Jawaharlal Nehru University, New Delhi 110067, India.
Murari
M
Singh
Department of Chemistry, Indian Institute of Technology-Delhi, New Delhi 110016, India.
Debdas
D
Dhabal
Department of Chemistry, The University of Utah, Salt Lake City, Utah 84112-0850, USA.
Andrew Huy
AH
Nguyen
Department of Chemistry, The University of Utah, Salt Lake City, Utah 84112-0850, USA.
Valeria
V
Molinero
Department of Chemistry, Indian Institute of Technology-Delhi, New Delhi 110016, India.
Charusita
C
Chakravarty