Application of 2D-IR spectroscopy to metalcarbonyls : photochemistry and isomerisation dynamics in solution

• Main Author: Kania, Rafal
• Published: University of Strathclyde 2012
• Subjects: 530
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.576359

The thesis presents work conducted by the author on the development of an ultrafast multidimensional infrared spectrometer, followed by studies of metalcarbonyl photochemical and isomerisation dynamics in solutions. The first chapter discusses fundamental concepts in chemical reactivity and dynamics, followed by the principles of steady state and time-resolved infrared spectroscopic methods as applied to studies of ultrafast chemical reactivity. The second chapter gives an account of the design and operation principles of the existing 2D-IR spectrometer followed by details of the development of UV-VIS frequency pump-probe experiment expanding the capacities of the in-house spectrometer toward ultrafast photochemistry via time-resolved infrared spectroscopy (TRIR). The third chapter reports the findings of TRIR studies of the photochemistry and ultrafast conformational isomerisation of a metallocarbonyl compound designed to mimic the active centre of the hydrogenase family of enzymes. The fourth chapter deals with ground state and UV-triggered ultrafast dynamic processes of triiron dodecacarbonyl (Fe3CO12) in n-heptane solution, with particular interest in the detection of fluxional behaviour related to CO bridge permutation. The fifth chapter demonstrates exhaustive structural and dynamical studies of a substituted metalcarbonyl catalyst using both 2D-IR and Transient 2D-IR spectroscopies both as tools for separation of multicomponent contributions to a complex infrared spectrum and analysis of relaxation dynamics. The sixth and final chapter presents work on the development of a vibrational echo 2D-IR spectrometer and associated software for spectrometer control and data processing.