Extending Benson Group Increment Theory to compounds of phosphorus, silicon, and boron with computational chemistry
A huge gap exists between the 200 million+ known chemical species listed in the Chemical Abstracts Service Registry and the few thousand compounds with data available in thermodynamic databases. In this work, high-level quantum chemical composite methods were applied to calculate thermodynamic properties for more than 300 compounds of phosphorus, silicon, and boron with little or no experimental data available. The acquired standard gas-phase enthalpies of formation, entropies, and heat capacities were compared to and contrasted with results from prior computational investigations as well as experimental studies. This revealed inconsistencies, outliers, and even systematic errors in the experimental data, with revised values suggested for thermodynamic properties of many fundamental small molecules. The data also enabled the derivation of new and updated group contribution values for almost 150 phosphorus-, silicon-, and boron-based groups within the framework of the Domalski-Hearing version of the Benson Group Increment Theory. These new values allow the thermodynamic properties of both existing and new chemical species of the three elements in question to be estimated quickly and inexpensively compared to the time and resources required if similar tasks were performed with quantum chemical methods of equal accuracy. Such advances in predictive methodology are highly valuable in many areas of chemical research and industry.
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Chemical Abstract Service on kemiallisten yhdisteiden tunnistenumerotietokanta, josta löytyy nykyään yli 200 miljoonaa tietuetta. Monien yhdisteiden ominaisuuksista ei kuitenkaan tiedetä paljoa ja esimerkiksi yhdisteiden termodynaamisia ominaisuuksia listaavissa taulukoissa on tyypillisesti vain muutamia tuhansia rivejä. Tässä työssä määritettiin tarkkojen kvanttikemiallisten yhdistelmämenetelmien avulla yli 300 fosforin, piin ja boorin yhdisteen termodynaamiset ominaisuudet, kuten niiden muodostumisentalpia, entropia ja ominaislämpökapasiteetti kaasufaasissa ja standarditilassa. Saatuja tuloksia verrattiin kokeelliseen dataan sekä aiempien laskennallisten tutkimusten tuloksiin. Tällä tavalla voitin osoittaa kokeellisesta datasta löytyvän runsaasti epäjohdonmukaisuuksia sekä myös karkeita ja systemaattisia virheitä. Monissa tapauksissa tutkimuksen tuottamat arvot yhdisteiden termodynaamisille ominaisuuksille ovat kokeellisia arvoja huomattavasti tarkempia, mikä puoltaa työn tulosten käyttämistä jatkosovelluksissa. Työssä määritettiin myös uudet ja päivitetyt Bensonin ryhmäkontribuutiot lähes 150:lle fosforin, piin ja boorin Bensonin ryhmälle käyttäen Domalskin ja Hearingin versiota Bensonin menetelmästä. Määritettyjen ryhmäkontribuutioiden avulla on mahdollista arvioida niin olemassa olevien kuin uusien kemiallisten yhdisteiden termodynaamisia ominaisuuksia nopeasti ja hyvällä tarkkuudella, mitä voidaan hyödyntää esimerkiksi monilla teollisuuden ja tutkimuksen aloilla.
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ISBN
978-951-39-9242-2ISSN Search the Publication Forum
2489-9003Contains publications
- Artikkeli I: Vuori, H., Rautiainen, M., Kolehmainen, E., & Tuononen, H. (2019). Benson group additivity values of phosphines and phosphine oxides : Fast and accurate computational thermochemistry of organophosphorus species. Journal of Computational Chemistry, 40(3), 572-580. DOI: 10.1002/jcc.25740. JYX: jyx.jyu.fi/handle/123456789/60895
- Artikkeli II: Vuori, H. T., Rautiainen, J. M., Kolehmainen, E. T., & Tuononen, H. M. (2022). High-Level Ab Initio Predictions of Thermochemical Properties of Organosilicon Species : Critical Evaluation of Experimental Data and a Reliable Benchmark Database for Extending Group Additivity Approaches. Journal of Physical Chemistry Part A, 126(10), 1729-1742. DOI: 10.1021/acs.jpca.1c09980
- Artikkeli III: Vuori, H. T., Rautiainen, J. M., Kolehmainen, E. T., & Tuononen, H. M. (2022). Computational thermochemistry : extension of Benson group additivity approach to organoboron compounds and reliable predictions of their thermochemical properties. Dalton Transactions, 51(41), 15816-15829. DOI: 10.1039/D2DT02659G
- Artikkeli IV: Vuori, H. T., Rautiainen, J. M., Kolehmainen, E. T., & Tuononen, H. M. (2022). Addition/Correction to “High-Level Ab Initio Predictions of Thermochemical Properties of Organosilicon Species: Critical Evaluation of Experimental Data and a Reliable Benchmark Database for Extending Group Additivity Approaches”. Journal of Physical Chemistry A, 126(10), 1729–1742. DOI: 10.1021/acs.jpca.2c05236
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