Descriptors for orientation, induction, hydrogen donor, and acceptor intermolecular forces in mono-component non-ionic compounds and bridges between cohesion, COSMO, and free energy scales
Abstract
Solubility parameters are important properties for various substances because they serve as descriptors of the different kinds of intermolecular forces. These parameters guide the selection of proper solvents for different applications and can aid in predicting the behavior of substances in these solvents. The present work develops several non-experimental methods for calculating such descriptors with improved accuracy and predictability. Proton donor, proton acceptor, orientation, and induction interactions contribute differently to the cohesion and solvation behavior of mono-component non-ionic compounds, but the corresponding fractional descriptors are generally not available from standard Hansen solubility parameter tables. We develop methods for estimating Karger--Snyder--Eon (KSE)-like cohesion-energy descriptors, δo, δi, δa, and δb, from tabulated HSP values and common molecular/solvent data. The calculated descriptors were tested against data published in literature and showed useful predictive accuracy in estimating missing or uncertain fractional cohesion parameters. The orientation and induction components were evaluated by three complementary approaches: Keesom/Debye based method, Clausius--Mossotti and Lorentz--Lorenz based method, and comparator selection in Hansen/KSE descriptor space. Some of these methods were also used to compare cohesion-energy descriptors δo, δi with free-energy-based descriptors γoγi. These comparisons show that the cohesion-energy and free-energy parameters are related but distinct thermodynamic descriptors. The donor/acceptor hydrogen-bond split was further compared across free-energy, cohesion-energy, and COSMO scales. Analysis of 73 mono-component non-ionic compounds gave a strong empirical relationship between the proton donor and acceptor products αGβG (free-energy framework), δaδb (cohesion-energy framework), and COSMO, supporting the conclusion that three descriptor pairs encode related but non-identical aspects of hydrogen bonding. This provides a bridge between cohesion-energy, free-energy, and COSMO descriptors and formulates a practical method for estimating, checking, and predicting fractional intermolecular-force descriptors when direct experimental data are unavailable.
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BibTeX
@misc{ostrovsky2026descriptors,
title = {{Descriptors for orientation, induction, hydrogen donor, and acceptor intermolecular forces in mono-component non-ionic compounds and bridges between cohesion, COSMO, and free energy scales}},
author = {Daniel A. Ostrovsky and Mikhail V. Ostrovsky},
howpublished = {ChemRxiv},
year = {2026},
month = aug,
doi = {10.26434/chemrxiv-2025-kd4z0/v3},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv-2025-kd4z0/v3},
note = {CC BY},
}
RIS
TY - UNPB
TI - Descriptors for orientation, induction, hydrogen donor, and acceptor intermolecular forces in mono-component non-ionic compounds and bridges between cohesion, COSMO, and free energy scales
AU - Daniel A. Ostrovsky
AU - Mikhail V. Ostrovsky
PY - 2026
DA - 2026/08/30
PB - ChemRxiv
DO - 10.26434/chemrxiv-2025-kd4z0/v3
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv-2025-kd4z0/v3
AB - Solubility parameters are important properties for various substances because they serve as descriptors of the different kinds of intermolecular forces. These parameters guide the selection of proper solvents for different applications and can aid in predicting the behavior of substances in these solvents. The present work develops several non-experimental methods for calculating such descriptors with improved accuracy and predictability. Proton donor, proton acceptor, orientation, and induction interactions contribute differently to the cohesion and solvation behavior of mono-component non-ionic compounds, but the corresponding fractional descriptors are generally not available from standard Hansen solubility parameter tables. We develop methods for estimating Karger--Snyder--Eon (KSE)-like cohesion-energy descriptors, δo, δi, δa, and δb, from tabulated HSP values and common molecular/solvent data. The calculated descriptors were tested against data published in literature and showed useful predictive accuracy in estimating missing or uncertain fractional cohesion parameters. The orientation and induction components were evaluated by three complementary approaches: Keesom/Debye based method, Clausius--Mossotti and Lorentz--Lorenz based method, and comparator selection in Hansen/KSE descriptor space. Some of these methods were also used to compare cohesion-energy descriptors δo, δi with free-energy-based descriptors γoγi. These comparisons show that the cohesion-energy and free-energy parameters are related but distinct thermodynamic descriptors. The donor/acceptor hydrogen-bond split was further compared across free-energy, cohesion-energy, and COSMO scales. Analysis of 73 mono-component non-ionic compounds gave a strong empirical relationship between the proton donor and acceptor products αGβG (free-energy framework), δaδb (cohesion-energy framework), and COSMO, supporting the conclusion that three descriptor pairs encode related but non-identical aspects of hydrogen bonding. This provides a bridge between cohesion-energy, free-energy, and COSMO descriptors and formulates a practical method for estimating, checking, and predicting fractional intermolecular-force descriptors when direct experimental data are unavailable.
ER -