COSMO Implementation in TURBOMOLE: Extension of an efficient quantum chemical code towards liquid systems

Schäfer, Ansgar; Klamt, Andreas; Sattel, Diana; Lohrenz, John C. W.; Eckert, Frank

doi:10.1039/b000184h

Cited by 672 publications

(636 citation statements)

References 35 publications

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“…Finally, a numerical approach was used to find the two compositions having equal chemical potentials of the three components (in the pseudobinary system) in the two phases at a particular temperature. The COSMO-RS calculations were carried at the BP/TZVP level (Turbomole, 57,58 DFT/COSMO calculation with the BP functional and TZVP 59 basis set using the optimized geometries at the same level of theory) and at the parameter file BP_TZ-VP_C21_0105. Figure 3 presents the liquid-liquid phase diagram between the [C 2 -C 8 mim][Tf 2 N] series and water and it should be noted the asymmetrical character of these binary systems behavior when adopting the mole fraction basis.…”

Section: Resultsmentioning

confidence: 99%

Mutual Solubilities of Water and the [C_nmim][Tf₂N] Hydrophobic Ionic Liquids

et al. 2008

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Ionic liquids (ILs) have recently garnered increased attention because of their potential environmental benefits as "green" replacements over conventional volatile organic solvents. While ILs cannot significantly volatilize and contribute to air pollution, even the most hydrophobic ones present some miscibility with water posing environmental risks to the aquatic ecosystems. Thus, the knowledge of ILs toxicity and their water solubility must be assessed before an accurate judgment of their environmental benefits and prior to their industrial applications. In this work, the mutual solubilities for [C 2 -C 8 mim][Tf 2 N] (n-alkyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide) and water between 288.15 and 318.15 K at atmospheric pressure were measured. Although these are among the most hydrophobic ionic liquids known, the solubility of water in these compounds is surprisingly large, ranging from 0.17 to 0.36 in mole fraction, while the solubility of these ILs in water is much lower ranging from 3.2 × 10 -5 to 1.1 × 10 -3 in mole fraction, in the temperature and pressure conditions studied. From the experimental data, the molar thermodynamic functions of solution and solvation such as Gibbs energy, enthalpy, and entropy at infinite dilution were estimated, showing that the solubility of these ILs in water is entropically driven. The predictive capability of COSMO-RS, a model based on unimolecular quantum chemistry calculations, was evaluated for the description of the binary systems investigated providing an acceptable agreement between the model predictions and the experimental data both with the temperature dependence and with the ILs structural variations.

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Section: Resultsmentioning

confidence: 99%

Mutual Solubilities of Water and the [C_nmim][Tf₂N] Hydrophobic Ionic Liquids

et al. 2008

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“…This step can be accomplished by a variety of tools, ranging from semi-empirical methods, as implemented in MOPAC (Stewart, 2009), to more sophisticated first-principle ones, implemented in many quantum chemistry software packages such as Gaussian (Barone and Cossi, 1998;Truong and Stefanovich, 1995), TURBOMOLE (Schäfer et al, 2000), DMol3 (Andzelm et al, 1995) and GAMESS (Baldridge and Klamt, 1997). The approximations considered in semi-empirical methods enable them to reduce the computing time by orders of magnitude (Gerber and Soares, 2010).…”

Section: Quantum Chemical Methodsmentioning

confidence: 99%

Assessing the reliability of predictive activity coefficient models for molecules consisting of several functional groups

Gerber

Soares

2013

Braz. J. Chem. Eng.

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-Currently, the most successful predictive models for activity coefficients are those based on functional groups such as UNIFAC. In contrast, these models require a large amount of experimental data for the determination of their parameter matrix. A more recent alternative is the models based on COSMO, for which only a small set of universal parameters must be calibrated. In this work, a recalibrated COSMO-SAC model was compared with the UNIFAC (Do) model employing experimental infinite dilution activity coefficient data for 2236 non-hydrogen-bonding binary mixtures at different temperatures. As expected, UNIFAC (Do) presented better overall performance, with a mean absolute error of 0.12 ln-units against 0.22 for our COSMO-SAC implementation. However, in cases involving molecules with several functional groups or when functional groups appear in an unusual way, the deviation for UNIFAC was 0.44 as opposed to 0.20 for COSMO-SAC. These results show that COSMO-SAC provides more reliable predictions for multifunctional or more complex molecules, reaffirming its future prospects.

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“…In some of the geometry optimisations, polar solvation effects were estimated by the conductor-like screening model (COSMO) [57,58]. These calculations were performed with default values for all parameters (implying a water-like probe molecule) and a dielectric constant of 80.…”

Section: Dft-d Calculationsmentioning

confidence: 99%

Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host–guest binding energies

Mikulskis

Cioloboc

Andrejić

et al. 2014

J Comput Aided Mol Des

220

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Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid hostguest binding energies. Link to publication Citation for published version (APA): Mikulskis, P., Cioloboc, D., Andrejić, M., Khare, S., Brorsson, J., Genheden, S., ... Ryde, U. (2014). Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host-guest binding energies. Journal of Computer-Aided Molecular Design, 28(4), 375-400. DOI: 10.1007/s10822-014-9739-x General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal AbstractWe have estimated free energies for the binding of nine cyclic carboxylate guest molecules to the octa-acid host in the SAMPL4 blind-test challenge with four different approaches. First, we used standard free-energy perturbation calculations of relative binding affinities, performed at the molecular-mechanics (MM) level with TIP3P waters, the GAFF force field, and two different sets of charges for the host and the guest, obtained either with the restrained electrostatic potential or AM1-BCC methods. Both charge sets give good and nearly identical results, with a mean absolute deviation (MAD) of 4 kJ/mol and a correlation coefficient (R 2 ) of 0.8 compared to experimental results. Second, we tried to improve these predictions with 28 800 density-functional theory (DFT) calculations for selected snapshots and the non-Boltzmann Bennett acceptance-ratio method, but this led to much worse results, probably because of a too large difference between the MM and DFT potential-energy functions. Third, we tried to calculate absolute affinities using minimised DFT structures. This gave intermediate-quality results with MADs of 5-9 kJ/mol and R 2 = 0.6-0.8, depending on how the structures were obtained. Finally, we tried to improve these results using local coupled-cluster calculations with single and double excitations, and non-iterative perturbative treatment of triple excitations (LCCSD(T0)), employing the polarisable multipole interactions with supermolecular pairs approach. Unfortunately, this only degraded the predictions, probably because a mismatch between the solvation energies obtained at the DFT and LCCSD(T0) levels.Key Words: binding affinities, host-guest, free-energies perturbation, density-functional calculations, CCSD(T), polarisable multipole interactions. 2 IntroductionOne of the largest challenges of computational chemistry is to predict the binding affinity of a small ligand to a larger receptor molecule, e.g. a drug candidate to its receptor prot...

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COSMO Implementation in TURBOMOLE: Extension of an efficient quantum chemical code towards liquid systems

Cited by 672 publications

References 35 publications

Mutual Solubilities of Water and the [C_nmim][Tf₂N] Hydrophobic Ionic Liquids

Mutual Solubilities of Water and the [C_nmim][Tf₂N] Hydrophobic Ionic Liquids

Assessing the reliability of predictive activity coefficient models for molecules consisting of several functional groups

Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host–guest binding energies

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COSMO Implementation in TURBOMOLE: Extension of an efficient quantum chemical code towards liquid systems

Cited by 672 publications

References 35 publications

Mutual Solubilities of Water and the [Cnmim][Tf2N] Hydrophobic Ionic Liquids

Mutual Solubilities of Water and the [Cnmim][Tf2N] Hydrophobic Ionic Liquids

Assessing the reliability of predictive activity coefficient models for molecules consisting of several functional groups

Free-energy perturbation and quantum mechanical study of SAMPL4 octa-acid host–guest binding energies

Contact Info

Product

Resources

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Mutual Solubilities of Water and the [C_nmim][Tf₂N] Hydrophobic Ionic Liquids

Mutual Solubilities of Water and the [C_nmim][Tf₂N] Hydrophobic Ionic Liquids