What question did this study set out to answer?

This research aims to improve the accuracy and reliability of calculated heats of formation (HOFs) for organophosphorus species using quantum-chemistry methods.

May 8, 2026

Filling the Gap of the Heats of Formation for Organophosphorus Species in the NIST Chemistry WebBook with Reliable Quantum-Chemistry Computations

Key Points

This research aims to improve the accuracy and reliability of calculated heats of formation (HOFs) for organophosphorus species using quantum-chemistry methods.
Applied revised atomic values for determining HOFs via atomization.
Utilized the combination of ωB97M-V and a revised vDZP basis set for calculations.
Parametrized methods for additional low-cost protocols in quantum chemistry.
Achieved good statistical accuracy in HOF data with the new computational approach.
The findings support enhanced predictions of thermochemical stability and chemical reactivity.
Demonstrated cost-effective methods suitable for extensive thermochemical assessments.

Abstract

group stabilizes the bonded phosphorus, while triple-bonded substituents tend to be thermochemically destabilizing. The atomic contributions are also shown to be useful for rationalizing reactivity, notably when thermochemical stability does not reflect chemical inertness. Furthermore, we have revised the optimal atomic values used for determining the HOFs by atomization with more economical methods and parametrized them for additional low-cost protocols. In particular, the combination of ωB97M-V and a revised vDZP basis set emerges as a good balance between cost and performance, making it suitable for obtaining an extensive set of HOF data with good statistical accuracy.

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Cite This Study

Bun Chan (Tue,) studied this question.

synapsesocial.com/papers/69fd7d94bfa21ec5bbf05e93 https://doi.org/https://doi.org/10.1021/acs.jpca.6c01968

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