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Original scientific paper

https://doi.org/10.5562/cca4247

DFT Approach to the Gibbs Energy of Hydride Anion in Acetonitrile by Modelling Hydricities

Zoran Glasovac ; Ruđer Bošković Institute, Division of organic chemistry and biochemistry, Bijenička c. 54, 10000, Zagreb, Croatia *
Borislav Kovačević ; Ruđer Bošković Institute, Division of physical chemistry, Bijenička c. 54, 10000, Zagreb, Croatia
Davor Margetić ; Ruđer Bošković Institute, Division of organic chemistry and biochemistry, Bijenička c. 54, 10000, Zagreb, Croatia

* Corresponding author.


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Abstract

Hydricity values for a range of non-metallic hydride donors were calculated using 25 different computational approaches, which included various density functionals and continuum solvent models. The quality of these results was assessed by comparing the computed data to experimental values, focusing on the correlation and deviation between them. The B2PLYP–D3 / CPCM-based methods demonstrated the best performance with ωB97xD / CPCM being only marginally behind. All methods show minimal influence from the size of the basis set, with correlations with correlation coefficients (r2) of 0.994 or higher. Comparable results were obtained whether the structures were optimized in the gas phase or in solution. The most significant errors were noted for borohydride derivatives. The correlation data were used to estimate the Gibbs energy of the hydride anion in acetonitrile (G*(H–)). The estimated value of –403.1 kcal mol–1 aligns well with the literature data.

Keywords

hydricity; DFT calculations; continuum solvation models; Gibbs energy; hydride anion

Hrčak ID:

348350

URI

https://hrcak.srce.hr/348350

Publication date:

21.5.2026.

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