catalysis; aqueous interfaces; organic synthesis; molecular dynamics; electronic structure; molecular systems
Elgabarty Hossam, Khaliullin Rustam, Kuhne Thomas (2015), Covalency of hydrogen bonds in liquid water can be probed by proton nuclear magnetic resonance experiments, in Nature Communications
, 6, 8318.
Kuehne Thomas D., Khaliullin Rustam Z. (2014), Nature of the Asymmetry in the Hydrogen-Bond Networks of Hexagonal Ice and Liquid Water, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
, 136(9), 3395-3399.
Karhan Kristof, Khaliullin Rustam, Kuehne Thomas (2014), On the role of interfacial hydrogen bonds in "on-water" catalysis, in Journal of Chemical Physics
, 141(22), 22D528.
Khaliullin Rustam Z., VandeVondele Joost, Hutter Juerg (2013), Efficient Linear-Scaling Density Functional Theory for Molecular Systems, in JOURNAL OF CHEMICAL THEORY AND COMPUTATION
, 9(10), 4421-4427.
Kuehne Thomas D., Khaliullin Rustam Z. (2013), Electronic signature of the instantaneous asymmetry in the first coordination shell of liquid water, in NATURE COMMUNICATIONS
, 4, 1450.
Khaliullin Rustam Z., Kuehne Thomas D. (2013), Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies, in PHYSICAL CHEMISTRY CHEMICAL PHYSICS
, 15(38), 15746-15766.
Doemer Manuel, Spura Thomas, Khaliullin Rustam Z., Kuehne Thomas D. (2013), Tetrahedral, when in fluid state, in NACHRICHTEN AUS DER CHEMIE
, 61(12), 1203-1206.
Zhang Chao, Khaliullin Rustam Z., Bovi Daniele, Guidoni Leonardo, Kuehne Thomas D. (2013), Vibrational Signature of Water Molecules in Asymmetric Hydrogen Bonding Environments, in JOURNAL OF PHYSICAL CHEMISTRY LETTERS
, 4(19), 3245-3250.
In nature aqueous surfaces and interfaces are ubiquitous and are involved in a wide variety of biological synthetic pathways. It is therefore remarkable that, up until recently, in vitro organic synthesis has mainly neglected water. This situation has been rapidly changing ever since Sharpless and co-workers demonstrated that many classes of organic transformations exhibit increased reaction rates, enhanced selectivity and improved yields when performed in heterogeneous water emulsions.A thorough understanding of the role that aqueous interfaces play in the catalytic phenomenon described by Sharpless et al. is crucial for designing effective laboratory and industrial-scale synthetic processes. However, obtaining detailed information about molecular-scale transformations at these interfaces interfaces represents a formidable challenge. Experimental investigation of complex dynamics of chemical species at liquid-liquid interfaces today is expensive, technically difficult, and often produces results without a clear interpretation. At the same time, computer simulations are either insufficiently accurate or so computationally demanding that studying interfacial processes on appropriate time and length scales is unfeasible. For these reasons, our knowledge of the mechanism of reactions in water emulsions is fragmentary and the origin of the catalytic effect at aqueous interfaces remains unclear.I propose a collaboration with Professor Kuhne at the University of Mainz in Germany with the goal of studying the microscopic origins of the enhanced reactivity phenomenon observed in heterogeneous water emulsions. To this end, I will develop and apply efficient and accurate methods for first-principle molecular dynamics simulations specifically tailored to take advantage of aspects of the electronic structure that are characteristic of molecular systems.The proposed research will provide well-founded input for a rational design of synthetic processes that can more effectively utilize the catalytic properties of aqueous interfaces. Furthermore, the developed computational algorithms will make completely new phenomena accessible in computer simulations. They can be immediately applied to study physico-chemical processes in molecular systems such as environmentally important chemical transformations at water surfaces in the atmosphere, the transport of ions and molecules across interfaces in phase-transfer catalysis and phase transitions in ionic liquids and liquid crystals. The theoretical advances in this work will also provide a mathematical foundation for the development of more sophisticated methods for computer simulations of solvation, association-dissociation, self-assembly and many other condensed phase phenomena in complex molecular systems of chemical, biochemical and nanotechnological interest.