Enthalpies of Sublimation of Organic and Organometallic Compounds. 1910–2001

Chickos, James S.; Acree, William E.

doi:10.1063/1.1475333

Cited by 516 publications

(479 citation statements)

References 12 publications

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“…This remains in the −43 to −47 kJ mol −1 experimental range which we favored in our earlier publication 1 due to several values being reported in this range. 59,60 The lattice energy of −51.6 kJ mol −1 also compares well to Beran's analysis 17 of the experimental data, deducing lattice energies of −52 ± 3 kJ mol −1 based on the experimental sublimation energies. Nevertheless, we expect the magnitude of the lattice energy to be slightly underestimated due to the neglect of two-body interactions beyond 9.4 Å in our earlier study.…”

Section: Scs-ccsd Scs(mi)-ccsd Ccsd(t) Scs-ccsd Error Scs(mi)-ccsd Errorsupporting

confidence: 55%

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Kennedy

McDonald

DePrince

et al. 2014

The Journal of Chemical Physics

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Coupled-cluster theory including single, double, and perturbative triple excitations [CCSD(T)] has been applied to trimers that appear in crystalline benzene in order to resolve discrepancies in the literature about the magnitude of non-additive three-body contributions to the lattice energy. The present results indicate a non-additive three-body contribution of 0.89 kcal mol −1 , or 7.2% of the revised lattice energy of −12.3 kcal mol −1 . For the trimers for which we were able to compute CCSD(T) energies, we obtain a sizeable difference of 0.63 kcal mol −1 between the CCSD(T) and MP2 three-body contributions to the lattice energy, confirming that three-body dispersion dominates over three-body induction. Taking this difference as an estimate of three-body dispersion for the closer trimers, and adding an Axilrod-Teller-Muto estimate of 0.13 kcal mol −1 for long-range contributions yields an overall value of 0.76 kcal mol −1 for three-body dispersion, a significantly smaller value than in several recent studies.

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Section: Scs-ccsd Scs(mi)-ccsd Ccsd(t) Scs-ccsd Error Scs(mi)-ccsd Errorsupporting

confidence: 55%

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Kennedy

McDonald

DePrince

et al. 2014

The Journal of Chemical Physics

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“…The latter data were determined by either direct calorimetric methods or calculated on the basis of the temperature dependence of measured infinite dilution activity coefficient data, and the published values were converted to gas-to-water and/or gas-to-octanol enthalpies of transfer by subtracting the solute's standard molar enthalpy of vaporization, 70 ∆ Vap H 298K°, or standard molar enthalpy of sublimation, 71 ∆ Sub H 298K°, at 298.15 K.…”

Section: Experimental Methodsmentioning

confidence: 99%

Enthalpy of Solvation Correlations for Gaseous Solutes Dissolved in Water and in 1-Octanol Based on the Abraham Model

Mintz

Clark

Acree

et al. 2006

J. Chem. Inf. Model.

116

102

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Data have been assembled on the enthalpies of solvation of 373 compounds in water and 138 compounds in 1-octanol. It is shown that an Abraham solvation equation with five descriptors can be used to correlate the experimental solvation enthalpies to within standard deviations of 3.68 kJ/mol (water) and 2.66 kJ/mol (1-octanol). The derived correlations provide very accurate mathematical descriptions of the observed enthalpies of solvation, which in the case of water span a range of 150 kJ/mol. Division of the experimental values into a training set and a test set shows that there is no bias in predictions and that the predictive capability of the correlations is better than 4 kJ/mol.

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“…The thermal contribution was evaluated at 298 K, the temperature to which most sublimation enthalpies are extrapolated. 54,55 The application of density functional perturbation theory 51 is not possible as it would require a fully self-consistent implementation of the TS vdW term, which is not currently available in the CASTEP code. The vibrational quantities for isolated molecules were also determined using phonon calculations.…”

Section: Estimation Of Vibrational Contributions To Sublimation Enmentioning

confidence: 99%

Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals

Reilly

Tkatchenko

2013

The Journal of Chemical Physics

298

498

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The development and application of computational methods for studying molecular crystals, particularly density-functional theory (DFT), is a large and ever-growing field, driven by their numerous applications. Here we expand on our recent study of the importance of many-body van der Waals interactions in molecular crystals [A. M. Reilly and A. Tkatchenko, J. Phys. Chem. Lett. 4, 1028 (2013)], with a larger database of 23 molecular crystals. Particular attention has been paid to the role of the vibrational contributions that are required to compare experiment sublimation enthalpies with calculated lattice energies, employing both phonon calculations and experimental heat-capacity data to provide harmonic and anharmonic estimates of the vibrational contributions. Exact exchange, which is rarely considered in DFT studies of molecular crystals, is shown to have a significant contribution to lattice energies, systematically improving agreement between theory and experiment. When the vibrational and exact-exchange contributions are coupled with a many-body approach to dispersion, DFT yields a mean absolute error (3.92 kJ/mol) within the coveted "chemical accuracy" target (4.2 kJ/mol). The role of many-body dispersion for structures has also been investigated for a subset of the database, showing good performance compared to X-ray and neutron diffraction crystal structures. The results show that the approach employed here can reach the demanding accuracy of crystal-structure prediction and organic material design with minimal empiricism. © 2013 AIP Publishing LLC. [http://dx

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Enthalpies of Sublimation of Organic and Organometallic Compounds. 1910–2001

Cited by 516 publications

References 12 publications

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Communication: Resolving the three-body contribution to the lattice energy of crystalline benzene: Benchmark results from coupled-cluster theory

Enthalpy of Solvation Correlations for Gaseous Solutes Dissolved in Water and in 1-Octanol Based on the Abraham Model

Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals

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