Theoretical calculation of enthalpy of formation of multiconformational molecules: 1,2-ethanediol, propanediols, and glycerol

Дорофеева, О. В.; Suchkova, Taisiya A.

doi:10.1016/j.cplett.2018.03.029

Cited by 9 publications

(9 citation statements)

References 21 publications

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“…This choice was made because Bolzmann averaging has been shown to lead to a correction that is similar in magnitude but opposite in sign to the correction for low-frequency internal rotations. 63 Hence, both corrections should be treated on equal footing, that is, either included or omitted. Considering the number of compounds investigated in this study and the level of theory employed, the calculation of these correction terms would have been a prohibitively expensive task.…”

Section: Computational Detailsmentioning

confidence: 99%

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

et al. 2022

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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.

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Section: Computational Detailsmentioning

confidence: 99%

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

et al. 2022

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“…So far, various theoretical methods for calculating the enthalpy of formation of compounds have been developed, such as the empirical method and the quantum chemical method. [20][21][22][23][24] Different from these traditional methods, this work predicted the enthalpy of formation of monosubstituted alkanes by using their values of 13 C NMR chemical shift. Its significance is not only to propose a new method to estimate the enthalpy of formation of monosubstituted alkanes, but also to establish a new method to understand the relationship between different properties based on the same molecular structure.…”

Section: F I G U R Ementioning

confidence: 99%

Estimation of the enthalpy of formation for monosubstituted alkanes by ¹³C NMR chemical shift

Tang

2020

J of Physical Organic Chem

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The quantitative relationship between the 13 C nuclear magnetic resonance (NMR) chemical shift and the enthalpy of formation of monosubstituted alkanes was studied, and a new approach for calculating enthalpy of formation was proposed. The experimental values of the enthalpy of formation of 64 monosubstituted alkanes were correlated with the parameters SCS (the sum of chemical shift), P3 (path counts of length three bonds), n (the number of C atoms), h[X] (the contributions of the substituent X to the Δ f H (RX)), and the product of IPI(X) (the interaction potential index) and PEI(R) (the polarizability effect index). The regression results show a good correlation (R = 0.9998, S = 4.5 kJ/mol). Its stability and prediction ability were confirmed by the results of the random sampling method and the leave-one-out method. In this paper, the 13 C NMR chemical shift and the enthalpy of formation of monosubstituted alkanes were associated quantitatively. The significance is not only to propose a new method to estimate the enthalpy of formation of monosubstituted alkanes, but also to establish a new method to understand the relationship between different properties based on a same molecular structure. Moreover, it provides a new approach for calculating a molecular difficult-to-test property parameter by means of another easy-to-test one. K E Y W O R D S chemical shift, enthalpy of formation, monosubstituted alkanes, 13 C NMR

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“…The products in the working reactions are conformationally similar to the reagent structures and this leads to the cancellation of errors associated with the conformational flexibility. Moreover, it has been shown that the conformer correction is partially compensated by the neglect of anharmonicity of low frequency torsional motions in the calculation of ZPVEs and thermal enthalpies …”

Section: Computational Detailsmentioning

confidence: 99%

“…Moreover, it has been shown that the conformer correction is partially compensated by the neglect of anharmonicity of low frequency torsional motions in the calculation of ZPVEs and thermal enthalpies. 105 2.3. Uncertainties of the Calculated Gas-Phase Enthalpies of Formation.…”

Section: Computational Detailsmentioning

confidence: 99%

Aliphatic Amines: A Critical Analysis of the Experimental Enthalpies of Formation by Comparison with Theoretical Calculations

2019

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The accuracy of experimental data on enthalpies of formation and vaporization of aliphatic amines (primary, secondary, and tertiary amines, di-, tri-, and tetramines, and cycloalkylamines) was assessed by theoretical calculations. The gas-phase enthalpies of formation were calculated using the Gaussian 4 (G4) method combined with isodesmic reactions. Three amines, CH 3 NH 2 , CH 3 NHCH 3 , and (CH 3 ) 3 N, were used as the main reference species in the isodesmic reactions; their experimental enthalpies of formation were recently revisited in the Active Thermochemical Tables. The enthalpies of vaporization were estimated by three group additivity and molecular electrostatic potential models and then were used to calculate the enthalpies of formation in the liquid state. When the deviations of experimental values from those provided by the theoretical methods were analyzed, a set of accurate and consistent values of enthalpy of formation of aliphatic amines was recommended for use in thermochemical calculations and as benchmarks for theoretical chemistry.

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Theoretical calculation of enthalpy of formation of multiconformational molecules: 1,2-ethanediol, propanediols, and glycerol

Cited by 9 publications

References 21 publications

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

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

Estimation of the enthalpy of formation for monosubstituted alkanes by ¹³C NMR chemical shift

Aliphatic Amines: A Critical Analysis of the Experimental Enthalpies of Formation by Comparison with Theoretical Calculations

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Theoretical calculation of enthalpy of formation of multiconformational molecules: 1,2-ethanediol, propanediols, and glycerol

Cited by 9 publications

References 21 publications

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

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

Estimation of the enthalpy of formation for monosubstituted alkanes by 13C NMR chemical shift

Aliphatic Amines: A Critical Analysis of the Experimental Enthalpies of Formation by Comparison with Theoretical Calculations

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Estimation of the enthalpy of formation for monosubstituted alkanes by ¹³C NMR chemical shift