Deuteration favours the polymorph with shorter O-H bonds: a stretch-bend rule tested across 220 inorganic polymorph pairs
Abstract
Deuteration can change which polymorph of a hydrogen-bonded crystal is stable. We derive a rule for the direction and size of this effect and test it across compounds. The H/D free-energy difference between two polymorphs is, to first order, ΔΔF ≈ S_str(1 − C)Δr̄, where Δr̄ is the difference in mean O-H length, S_str ≈ ½hc(1 − 1/ρ)s at room temperature comes from the softening s of the O-H stretch with bond length, and C is the fraction of the stretch term cancelled by bend and libration. While C < 1, deuteration favours the polymorph with the shorter O-H bonds, that is, with the weaker hydrogen bonds; where C(T) crosses unity the preference reverses. In harmonic calculations with three universal machine-learned potentials on 220 inorganic polymorph pairs, ΔΔF rises by 0.11 to 0.13 meV per H per mÅ at 300 K, with C about one half. For moderate to strong hydrogen bonds (a boundary chosen after inspecting the data) the rule is right in 74 of 84 pairs and 27 of 28 formulas; the exceptions share one Al(OH)₃ structure in which bend and libration outweigh the stretch at room temperature (C > 1 in two of the three models). The rule fails for weak hydrogen bonds and did not transfer in a prospective test on new pairs. Exploratory quasi-harmonic calculations put the diaspore to δ-AlOOH transition about 1 GPa higher for AlOOD than for AlOOH, a shift that high-pressure experiments can test.
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BibTeX
@misc{erganis2026deuteration,
title = {{Deuteration favours the polymorph with shorter O-H bonds: a stretch-bend rule tested across 220 inorganic polymorph pairs}},
author = {Muhammet Can Erganiş},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011133/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011133/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Deuteration favours the polymorph with shorter O-H bonds: a stretch-bend rule tested across 220 inorganic polymorph pairs
AU - Muhammet Can Erganiş
PY - 2026
DA - 2026/10/27
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011133/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011133/v1
AB - Deuteration can change which polymorph of a hydrogen-bonded crystal is stable. We derive a rule for the direction and size of this effect and test it across compounds. The H/D free-energy difference between two polymorphs is, to first order, ΔΔF ≈ S_str(1 − C)Δr̄, where Δr̄ is the difference in mean O-H length, S_str ≈ ½hc(1 − 1/ρ)s at room temperature comes from the softening s of the O-H stretch with bond length, and C is the fraction of the stretch term cancelled by bend and libration. While C < 1, deuteration favours the polymorph with the shorter O-H bonds, that is, with the weaker hydrogen bonds; where C(T) crosses unity the preference reverses. In harmonic calculations with three universal machine-learned potentials on 220 inorganic polymorph pairs, ΔΔF rises by 0.11 to 0.13 meV per H per mÅ at 300 K, with C about one half. For moderate to strong hydrogen bonds (a boundary chosen after inspecting the data) the rule is right in 74 of 84 pairs and 27 of 28 formulas; the exceptions share one Al(OH)₃ structure in which bend and libration outweigh the stretch at room temperature (C > 1 in two of the three models). The rule fails for weak hydrogen bonds and did not transfer in a prospective test on new pairs. Exploratory quasi-harmonic calculations put the diaspore to δ-AlOOH transition about 1 GPa higher for AlOOD than for AlOOH, a shift that high-pressure experiments can test.
ER -