Investigation of liquids, solvents and solvent effects with modern theoretical methods

摘要

It is the aim of this work to elucidate the usefulness and feasibility of the first-principles approach and to extend it to the regime of liquid molecular substances of complex structure. Physical and thermodynamic properties of complicated liquids are investigated by means of Car–Parrinello molecular dynamics (CPMD) and also with static quantum chemical methods. The connection between the dynamic and static approach is given by the quantum cluster equilibrium (QCE) theory. Since the QCE theory is not yet well established, a new implementation in the MD post-processing program PEACEMAKER is presented. It can be shown that it is by far more important to include cooperative effects rather than to concentrate the effort on the inclusion of weak dispersion forces not present in current density functionals. Traditionally, investigations of complicated liquids were also undertaken with the tools of simple liquids, because for some problems the size of the system does not allow for a more accurate description. Although linear-scaling techniques are simplifications from the point of view of quantum chemistry, they might be severe improvements when compared to traditional molecular dynamics simulations. For the interpretation of the liquid state the introduction of local properties is inevitable. New methods are presented for the calculation of local dipole moments and for the estimation of hydrogen bond energies in quantum mechanically nondecomposable systems. The latter also allows for the detection of hydrogen bonds in simulations through a wavefunction-based criterion instead of one which is solely grounded on the geometric structure of the atomic nuclei involved. The article then discusses prominent liquids which show properties that are not yet understood. Another part of the work analyzes the effect of solvent molecules on solutes and their reactions in the solvent. Finaly, neoteric solvents, such as ionic liquids are discussed.