Computational Prediction of Thermodynamic Properties of Organic Molecules in Aqueous Solutions

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We showed that the poor accuracy of hydration thermodynamics calculations with a molecular integral equation theory, Reference Interaction Site Model (RISM), can be considerably improved with a set of molecular structural corrections. In this thesis we developed a novel hybrid RISM-based method for calculation of hydration thermodynamics, the Structural Descriptors Correction (SDC) model (RISM-SDC). The method uses a thermodynamic quantity obtained by RISM as an initial approximation and a set of corrections to decrease the error of the calculated parameter. Each correction in the RISM-SDC model can be represented as a structural descriptor (Di) multiplied by the corresponding correction coefficient (ai). One important descriptor (D1) is the dimensionless partial molar volume calculated by RISM. The rest of the structural descriptors correspond to the number of specific molecular fragments (double bonds, aromatic rings, electron-donating/withdrawing substituents, etc.). The correction coefficients {ai} are found by training the model on a set of monofunctional compounds. For the first time, we showed that the RISM-SDC model allows to achieve the chemical accuracy of solvation thermodynamics predictions within the RISM approach, that has been a challenge for over 40 years. In this thesis we demonstrated the high efficiency of the RISM-SDC model for predicting important hydration thermodynamic quantities, hydration free energy (HFE) and partial molar volume (PMV).
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Wissenschaftliche Abschlussarbeiten » Dissertation
Fakultät / Institut:
Fakultät für Chemie
iTunes U Categories:
Science » Chemistry
Dewey Dezimal-Klassifikation:
500 Naturwissenschaften und Mathematik » 540 Chemie » 541 Physikalische Chemie
integral equation theory, RISM, structural descriptors correction (SDC), hydration free energy, partial molar volume
Dr. Fedorov, Maxim [Thesis advisor]
Prof. Dr. Spohr, Eckhard [Reviewer]
Prof. Dr. Bopp, Philippe A. [Reviewer]
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