Temperature Dependence of Hydrogen Bond Networks of Liquid Water: Thermodynamic Properties and Structural Heterogeneity from Topological Descriptors

Paulo M C de Oliveira; Jéssica I R de Souza; Juliana A B da Silva; Ricardo L Longo

doi:10.1021/acs.jpcb.2c08873

Temperature Dependence of Hydrogen Bond Networks of Liquid Water: Thermodynamic Properties and Structural Heterogeneity from Topological Descriptors

J Phys Chem B. 2023 Mar 16;127(10):2250-2257. doi: 10.1021/acs.jpcb.2c08873. Epub 2023 Mar 6.

Authors

Paulo M C de Oliveira¹, Jéssica I R de Souza², Juliana A B da Silva^{1

3}, Ricardo L Longo^{2

4}

Affiliations

¹ Núcleo Interdisciplinar de Ciências Exatas e da Natureza, Campus do Agreste. Universidade Federal de Pernambuco, 55.014-900 Caruaru, Pernambuco, Brazil.
² Programa de Pós-Graduação em Ciência de Materiais, Universidade Federal de Pernambuco, 50740-560 Recife, Pernambuco, Brazil.
³ Programa de Pós-Graduação em Química, Universidade Federal Rural de Pernambuco, 52.171-900 Recife, Pernambuco, Brazil.
⁴ Departamento de Química Fundamental, Universidade Federal de Pernambuco, 50740-540 Recife, Pernambuco, Brazil.

PMID: 36877152
DOI: 10.1021/acs.jpcb.2c08873

Abstract

Topological analyses of hydrogen bond networks were performed based on the complex network and island statistics of liquid water at different temperatures. The influence of temperature on the liquid water structures and the topological properties of the hydrogen bond networks was investigated by Metropolis Monte Carlo simulations with the TIP4P/2005 potential model. The bilinear behavior of the second peak in the radial distribution function with the temperature was properly reproduced by these simulations. The average connectivity also displayed a bilinear behavior consistent with being a local descriptor. The semiglobal average path length (or geodesic distance) descriptor showed an unprecedented trimodal distribution, whose areas were dependent on the temperature. Considering equilibrium between these three sets of networks, standard enthalpy and entropy of equilibrium were determined for the first time, providing new insights into the structural heterogeneities of liquid water with interesting perspectives for modeling these quantitative properties of hydrogen bond networks.