Molecular origin of the well-known specific heat anomaly in supercooled liquid water is investigated here by using extensive computer simulations and theoretical analyses. A rather sharp increase in the values of isobaric specific heat with lowering temperature and the weak temperature dependence of isochoric specific heat in the same range are reproduced in simulations. We calculated the spatio-temporal correlation among temperature fluctuations and examined the frequency dependent specific heat. The latter shows a rapid growth in the low frequency regime as temperature is cooled below 270 K. In order to understand the microscopic basis of this increase, we have performed a shellwise decomposition of contributions of distant molecules to the temperature fluctuations in a central molecule. This decomposition reveals the emergence, at low temperatures, of temporally slow, spatially long ranged large temperature fluctuations. The temperature fluctuation time correlation function (TFCF) can be fitted to a William-Watts stretched exponential form with the stretching parameter close to 0.6 at low temperatures, indicating highly non-exponential relaxation. Temperature dependence of the relaxation time of the correlation function can be fitted to Vogel-Fulcher-Tamermann expression which provides a quantitative measure of the fragility of the liquid. Interestingly, we find that the rapid growth in the relaxation time of TFCF with lowering temperature undergoes a sharp crossover from a markedly fragile state to a weakly fragile state around 220 K.
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7 March 2013
Research Article|
March 05 2013
Frequency dependence of specific heat in supercooled liquid water and emergence of correlated dynamics
Shinji Saito;
Shinji Saito
a)
1
Institute for Molecular Science
, Myodaiji, Okazaki, Aichi 444-8585, Japan
and The Graduate University for Advanced Studies
, Myodaiji, Okazaki, Aichi 444-8585, Japan
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Iwao Ohmine;
Iwao Ohmine
b)
1
Institute for Molecular Science
, Myodaiji, Okazaki, Aichi 444-8585, Japan
and The Graduate University for Advanced Studies
, Myodaiji, Okazaki, Aichi 444-8585, Japan
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Biman Bagchi
Biman Bagchi
c)
2
Indian Institute of Science
, Bangalore 560012, India
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a)
Electronic mail: shinji@ims.ac.jp.
b)
Electronic mail: ohmine@ims.ac.jp.
c)
Electronic mail: bbagchi@sscu.iisc.ernet.in.
J. Chem. Phys. 138, 094503 (2013)
Article history
Received:
December 05 2012
Accepted:
February 13 2013
Citation
Shinji Saito, Iwao Ohmine, Biman Bagchi; Frequency dependence of specific heat in supercooled liquid water and emergence of correlated dynamics. J. Chem. Phys. 7 March 2013; 138 (9): 094503. https://doi.org/10.1063/1.4793555
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