Benchmarking Experimental and Computational Thermochemical Data: A Case Study of the Butane Conformers

• Published in: Journal of chemical theory and computation Vol. 8; no. 2; pp. 479 - 486
• Main Authors: Barna, Dóra, Nagy, Balázs, Csontos, József, Császár, Attila G, Tasi, Gyula
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 14.02.2012
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/ct2007956

Due to its crucial importance, numerous studies have been conducted to determine the enthalpy difference between the conformers of butane. However, it is shown here that the most reliable experimental values are biased due to the statistical model utilized during the evaluation of the raw experimental data. In this study, using the appropriate statistical model, both the experimental expectation values and the associated uncertainties are revised. For the 133–196 and 223–297 K temperature ranges, 668 ± 20 and 653 ± 125 cal mol–1, respectively, are recommended as reference values. Furthermore, to show that present-day quantum chemistry is a favorable alternative to experimental techniques in the determination of enthalpy differences of conformers, a focal-point analysis, based on coupled-cluster electronic structure computations, has been performed that included contributions of up to perturbative quadruple excitations as well as small correction terms beyond the Born–Oppenheimer and nonrelativistic approximations. For the 133–196 and 223–297 K temperature ranges, in exceptional agreement with the corresponding revised experimental data, our computations yielded 668 ± 3 and 650 ± 6 cal mol–1, respectively. The most reliable enthalpy difference values for 0 and 298.15 K are also provided by the computational approach, 680.9 ± 2.5 and 647.4 ± 7.0 cal mol–1, respectively.