Large-scale calculations of ionic liquids
thesisposted on 27.02.2017, 02:36 authored by Rigby, Jason David
Ionic liquids (ILs) hold great promise in many fields including energy storage and generation, mechanical, pharmaceutical, synthetic and separation applications to name just a few. For any given application, the desired physical properties of the ideal IL may differ substantially from others and no widely applicable patterns or trends to facilitate intuitive design. The origins of physical properties lie in the characteristics of the intermolecular energetics, which consist of a complex interplay between electrostatic and dispersion forces. This thesis investigates and develops computational methodologies for calculating a reliable description of the intermolecular interactions for this challenging class of solvents and electrolytes of the future. The electrostatic approximation used in classical molecular dynamics (MD) where atomic partial charges are assigned was investigated in terms of methods based on density matrix partitioning, and the restrained electrostatic potentials (RESP) approaches. It was found that the “geodesic” atomic partial charge scheme, part of the RESP family, produced the most accurate charges. This was measured in terms of (a) charge convergence with increasing basis set size; (b) charge invariance with changes to the coordinate system; (c) insensitivity to minor structural changes on the resulting charges; (d) adequate capture of charge transfer effects; and (e) the preservation of symmetric of charges in symmetric molecules. Although charges can vary dramatically depending on the scheme used, the careful use of atomic partial charge schemes may still produce reliable forcefields, or at least serve as a rapid diagnostic tool to quantify electrostatic interactions and charge transfer. In moving towards unbiased a priori descriptions of IL intermolecular interactions, second-order Møller-Plesset perturbation theory (MP2) was used with the linear-scaling fragment molecular orbital (FMO) framework to assess the extent to which dispersion forces play a role in the intermolecular energetics. ILs of increasing size were examined such that the many-body effects may be captured. The dispersion energy contribution formed up to 20% of the total interaction energy. Furthermore, the interaction energy as produced by FMO was within 1 kJ mol−1 of the full-wavefunction MP2 interaction energy when three-body effects were included. As the dispersion interaction is purely a quantum mechanical phenomenon, correlated quantum mechanical methods, such as MP2 or coupled-cluster approaches, are required to provide an unbiased account of these effects. Ab initio methods such as MP2 and CCSD(T) scale formally as N⁵ an N⁷, respectively, with chemical system size. While the FMO approach provides a marked improvement in efficiency, the counterpoise (CP) approach to correcting the basis set superposition error (BSSE) is not amenable to fragmented approaches and requires each ion in the cluster to be calculated in the basis set of the entire system. In order to remove this bottleneck, the spin-component scaled second-order Møller Plesset perturbation theory (SCS-MP2) methodology was refined by fitting 174 non-CP corrected interaction energies at the MP2/cc-pVTZ level of theory to CP corrected CCSD(T)/CBS benchmark energies. This has resulted in an implicit BSSE correction that may be used within the highly efficient FMO framework, and is shown to yield results on par with or exceeding the accuracy of MP2/cc-pVQZ for clusters of two and four ion pairs (IPs). This new approach as been termed SCS-IL-MP2. An alternative dispersion corrected density functional theory (DFT) approach, DFT- D3, was assessed and refined in view of producing accurate interaction energies at the same CCSD(T)/CBS quality. The same test set of 174 ILs was used to fit the SCS-IL-MP2 approach was used to refit the DFT-D3 approach for both the Hartree-Fock (HF) wavefunction and the PBE and BLYP density functionals (DFs). In most cases, the selection of the DF and associated DFT-D version 3 (DFT-D3) parameters differed negligibly with all reaching within 1 to 2 kJ mol−1 per IP. HF-D3 parameters, on the other hand, showed a substantial improvement, particularly when used with the Becke-Johnson (BJ) damping function. Refitted HF-D3 and the BJ damping function was able to consistently provide interaction energy errors below 5 kJ mol−1 per IP. It would be worthwhile further investigating the application of the refined HF-D3 in its ability to produce reliable energies and geometries over a more diverse set of ILs. Both the SCS-IL-MP2 and new DFT-D3 approaches may be applied to the highly scal- able FMO framework. These form the core elements of the quantum chemistry toolbox for the study and understanding of the physicochemical properties of ILs that have so far been only superficially characterised by electronic structure theory. From this starting point, a rigorous and unbiased a priori understanding of the intermolecular interactions and resulting physicochemical properties may be predicted by means of efficient ab initio molecular dynamics (AIMD) techniques.