A resolution for the enigma of a liquid’s configurational entropy-molecular kinetics relation
Bibliographic record
Abstract
The literature data on the entropy and heat capacity of 33 glass-forming liquids have been used to examine the validity of the Adam–Gibbs relation between a liquid’s configurational entropy, Sconf, and its molecular kinetics. The critical entropy, sc*, of kB ln 2 (=0.956×10−23 J molecule−1 K−1) in the equation is less than even the residual entropy per molecule in a glass at 0 K, and this creates difficulties in determining the size of the cooperatively rearranging region, z*, in the liquid. It is argued that, z*=[1−(T0/T)]−1, and the temperature-invariant energy term, Δμ, is equal to RB, which has been determined from the knowledge of the Vogel–Fulcher–Tamman parameters B and T0, with R being the gas constant, and on the basis of the argument that the preexponential term of this equation is identical to that of the Adam–Gibbs relation. As the lattice modes in a glass are lower in frequency and more anharmonic than in its crystal, its vibrational entropy, Svib, would be higher than that of the crystal phase. Therefore, Sconf of a glass (and liquid) is significantly less than the difference between the entropy of the glass (and liquid) and the entropy of its completely ordered crystal phase. Both quantities, Svib and Sconf, have been estimated without reference to the vibrational spectra. The conclusions can be tested by determining z* and Δμ from measurements of the dielectric spectra of a liquid confined to nanometer-size pores. This is elaborated by a calculation for 3-bromopentane.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.008 | 0.014 |
| Meta-epidemiology (narrow) | 0.002 | 0.001 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.003 | 0.001 |
| Science and technology studies | 0.003 | 0.026 |
| Scholarly communication | 0.006 | 0.033 |
| Open science | 0.003 | 0.010 |
| Research integrity | 0.005 | 0.019 |
| Insufficient payload (model declined to judge) | 0.005 | 0.001 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".