Free Energy of Metals from Quasi-Harmonic Models of Thermal Disorder

A simple modeling method to extend first-principles electronic structure calculations to finite temperatures is presented. The method is applicable to crystalline solids exhibiting complex thermal disorder and employs quasi-harmonic models to represent the vibrational and magnetic free energy contributions. The main outcome is the Helmholtz free energy, calculated as a function of volume and temperature, from which the other related thermophysical properties (such as temperature-dependent lattice and elastic constants) can be derived. Our test calculations for Fe, Ni, Ti, and W metals in the paramagnetic state at temperatures of up to 1600 K show that the predictive capability of the quasi-harmonic modeling approach is mainly limited by the electron density functional approximation used and, in the second place, by the neglect of higher-order anharmonic effects. The developed methodology is equally applicable to disordered alloys and ordered compounds and can therefore be useful in modeling realistically complex materials.

The Second Law and Entropy Misconceptions Demystified

The challenges and claims of hypothetical violations of the Second Law of thermodynamics have been a topic of many scientific, philosophical and social publications, even in the most prestigious scientific journals. Fascination with challenging the Second Law has further accelerated throughout the development of statistical and quantum physics, and information theory. It is phenomenologically reasoned here that non-equilibrium, useful work-energy potential is always dissipated to heat, and thus thermodynamic entropy (a measure of thermal disorder, not any other disorder) is generated always and everywhere, at any scale without exception, including life processes, open systems, micro-fluctuations, gravity or entanglement. Furthermore, entropy cannot be destroyed by any means at any scale (entropy is conserved in ideal, reversible processes and irreversibly generated in real processes), and thus, entropy cannot overall decrease, but only overall increase. Creation of ordered structures or live species always dissipate useful energy and generate entropy, without exception, and thus without Second Law violation. Entropy destruction would imply spontaneous increase in non-equilibrium, with mass-energy flux displacement against cause-and-effect, natural forces, as well as negate the reversible existence of the very equilibrium. In fact, all resolved challengers’ paradoxes and misleading violations of the Second Law to date have been resolved in favor of the Second Law and never against. We are still to witness a single, still open Second Law violation, to be confirmed.

Spins and Magnets

The magnetization of iron is the result of an energetically favorable alignment of adjacent spins. At high temperatures, the thermal motion prevents such alignment, but below a certain specific (Curie) temperature, the energy constraints overcome the thermal disorder trend. The onset of magnetization is abrupt, it defines a critical point. The resulting Curie temperature thus separates the high temperature paramagnetic from the low temperature ferromagnetic state.

Statistical Complexity of the Coriolis Antipairing Effect

Using the entropic quantifier called statistical complexity, we investigate the interplay between (1) pairing interactions between fermions, can be viewed as analogous with superconductivity based on Cooper pairs; (2) rotations of the system as a whole around an axis; and (3) thermal excitations. Two different ordering processes are at work: alignment and pairing of two fermions to total spin zero. They compete among themselves and with thermal disorder. A complex physics ensues as a consequence. The existence of novel phenomena is revealed by the behavior of the statistical complexity. In particular, it is seen how order can arise out of disorder in originating high-temperature superconductivity.