Structure and Reactivity of Functional Molecules on Surfaces

Who: Reinhard J. Maurer, Yale University
Thursday, February 9, 2017 - 4:00pm to 5:00pm
Scaife Hall 220

Fundamental understanding of molecular structure and chemical reactivity at complex interfaces is key to many technological applications ranging from single molecule electronics to functional surfaces. An important goal of molecular nanotechnology is to manipulate single molecules in well-defined chemical environments. Using electronic structure methods, we study prototypical example systems such as azobenzene [1] and porphyrine [2] derivatives adsorbed on well-defined single crystal metal surfaces. Hereby the focus lies on the effects of molecule functionalization, substrate reactivity, finite- temperature, and surface coverage on measurable structural and electronic properties of adsorbates. By accurately accounting for chemical interactions and thermal fluctuations in adsorbate structure and energetics, we directly simulate the experimental observables of Temperature Programmed Desorption and X-ray Spectroscopy measurements. On the example of photo-induced isomerization of azobenzene, key parameters and molecular design principles will be discussed that govern molecular function on metallic surfaces. Finally, the intrinsically non-adiabatic mechanistic details of molecular reactions on metal surfaces are addressed using recently developed methods to study electronic excited states [3] and vibrational energy dissipation [4].

[1] Maurer, Reuter, Angew. Chem. Int. Ed. 51, 12009-12011 (2012)
[2] Müller, Diller, Maurer, Reuter, J. Chem. Phys. 144, 024701 (2016)
[3] Maurer, Reuter, J. Chem. Phys. 139, 014708 (2013)
[4] Askerka, Maurer, Batista, Tully, Phys. Rev. Lett. 116, 217601 (2016)