A1 Journal article (refereed)
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 (2022)


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. https://doi.org/10.1021/acs.jpca.1c09980


JYU authors or editors


Publication details

All authors or editorsVuori, Hannu T.; Rautiainen, J. Mikko; Kolehmainen, Erkki T.; Tuononen, Heikki M.

Journal or seriesJournal of Physical Chemistry Part A

ISSN1089-5639

eISSN1520-5215

Publication year2022

Publication date07/03/2022

Volume126

Issue number10

Pages range1729-1742

PublisherAmerican Chemical Society (ACS)

Publication countryUnited States

Publication languageEnglish

DOIhttps://doi.org/10.1021/acs.jpca.1c09980

Publication open accessOpenly available

Publication channel open accessPartially open access channel

Publication is parallel published (JYX)https://jyx.jyu.fi/handle/123456789/80227

Additional informationAddition/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”. doi: 10.1021/acs.jpca.2c05236 ; https://doi.org/10.1021/acs.jpca.2c05236


Abstract

A high-level composite quantum chemical method, W1X-1, is used herein to calculate the gas-phase standard enthalpy of formation, entropy, and heat capacity of 159 organosilicon compounds. The results set a new benchmark in the field that allows, for the first time, an in-depth assessment of existing experimental data on standard enthalpies of formation, enabling the identification of important trends and possible outliers. The calculated thermochemical data are used to determine Benson group additivity contributions for 60 Benson groups and group pairs involving silicon. These values allow fast and accurate estimation of thermochemical parameters of organosilicon compounds of varying complexity, and the data acquired are used to assess the reliability of experimental work of Voronkov et al. that has been repeatedly criticized by Becerra and Walsh. Recent results from other computational investigations in the field are also carefully discussed through the prism of reported advancements.


Keywordsorganometallic compoundssiliconthermochemistryquantum chemistry


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Ministry reportingYes

Reporting Year2022

JUFO rating1


Last updated on 2024-25-02 at 17:15