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

Vuori, Hannu
Rautiainen, Mikko
Kolehmainen, Erkki
Tuononen, Heikki

Publication details

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

Journal or series: Journal of Physical Chemistry Part A

ISSN: 1089-5639

eISSN: 1520-5215

Publication year: 2022

Publication date: 07/03/2022

Volume: 126

Issue number: 10

Pages range: 1729-1742

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

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

Publication open access: Openly available

Publication channel open access: Partially open access channel

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

Additional information: 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”. 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.

Keywords: organometallic compounds; silicon; thermochemistry; quantum chemistry

Fields of science: