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Thermal Excitation

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The Attribute of Water

Part of the book series: Springer Series in Chemical Physics ((CHEMICAL,volume 113))

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Abstract

Characterized by the Debye temperature that is proportional to the characteristic phonon frequency and by the thermal integration that is proportional to the segmental cohesive energy, the specific-heat for the O:H nonbond differs from that of the H–O bond. The thermodynamic disparity of the O:H and the H–O defines the cooperative angle-length-stiffness relaxation of the O:H–O bond in four different ways, which is responsible for the density and phonon-stiffness oscillation of water and ice in the full temperature range. Generally, cooling shortens and stiffens the part of relatively lower specific-heat, and meanwhile, lengthens and softens the other part of the O:H–O bond via O–O repulsion. Length contraction/elongation of a specific part always stiffens/softens its corresponding phonon. The O–O distance is longer in ice than it is in water, resulting in a lower density, so that ice floats. Phonon spectrometrics enabled the molecular-site-resolved O:H–O bond relaxation dynamics in terms of segmental length and stiffness, order of molecular fluctuation, and the abundance of phonons.

• A superposition of the O:H and H–O specific heats defines two intersecting temperatures that divide the full temperature range into four regimes of different specific-heat ratios, which facilitates density oscillation in the phase of liquid, quasisolid, ice I h+c , and ice XI.

• The segment of relatively lower specific heat serves as the “master” to follow the regular rule of thermal expansion, which drives the other “slave” segment to relax oppositely when they are subject to heating or cooling.

• Cooling shortens the O:H nonbond more than H–O expands in the liquid and the I h+c phase, which results in the seemingly “normal” thermal expansion of water and ice. The H–O bond and the O:H exchange roles in the quasisolid phase resulting in the negative thermal expansion of the quasisolid, which makes ice floats.

• Heating fluctuates the H–O radicals with increased abundance and redshift; the skin is thermally more stable than the bulk that undergoes H-O bond heating blueshift.

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Authors and Affiliations

  1. School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore, Singapore

    Chang Q. Sun

  2. Xiangtan University, Changsha, China

    Yi Sun

  3. China Jiliang University, Hangzhou, China

    Yi Sun

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Sun, C.Q., Sun, Y. (2016). Thermal Excitation. In: The Attribute of Water. Springer Series in Chemical Physics, vol 113. Springer, Singapore. https://doi.org/10.1007/978-981-10-0180-2_7

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