Transient Changes in Molecular Geometries and How to Model Them

This thesis examines various aspects of excess excitation energy dissipation via dynamic changes in molecular structure, vibrational modes and solvation. The computational work is carefully described and the results are compared to experimental data obtained using femtosecond spectroscopy and x-ray scattering. The level of agreement between theory and experiment is impressive and provides both a convincing validation of the method and significant new insights into the chemical dynamics and molecular determinants of the experimental data. Hence, the method presented in the thesis has the potential to become a very important contribution to the rapidly growing field of femtosecond x-ray science, a trend reflected in the several free-electron x-ray lasers (XFELs) currently being built around the world.

Light-induced chemical processes are accompanied by molecular motion of electrons and nuclei on the femtosecond time scale. Uncovering these dynamics is central to our understanding of the chemical reaction on a fundamental level.

Asmus O. Dohn has implemented a highly efficient QM/MM Direct Dynamics method for predicting the solvation dynamics of transition metal complexes in solution.

Nominated as an outstanding Ph.D. thesis by the Technical University of Denmark, Denmark Includes useful, hands-on guides and sample scripts for newcomers to the method Provides a thorough description of how to calculate X-ray solution scattering signals on the basis of molecular dynamics (MD) simulations, connecting theory/simulation and experimentation Includes a wealth of illustrations Includes supplementary material: sn.pub/extras

Autorentext
Asmus O. Dohn studied Nano science at the University of Copenhagen, where he focused on structural properties of metallic complexes in solution, analyzed through x-ray and simulation-based methods. He obtained his Masters degree in 2011 with the highest remarks and was awarded the PhD-School Pre-Doc scholarship, for students especially suited for academic careers. He has also worked for the Nano-Science Center on communication/dissemination tasks, both directed towards the general public and for grant applications. His PhD studies included participating in a significant amount of experimental beam times at XFELs and synchrotrons, as well as a stay at the University of Iceland, working on the implementation of more advanced force-fields.

Inhalt
Introduction and Background.- Treating Relativistic Effects in Transition Metal Complexes.- X-Ray Scattering from Purely Classical MD.- Direct Dynamic Simulations of Ir2(Dimen)4(2+).-Directs Dynamics Simulations of the Ru=Co Complex.- Summary.- Appendix.