Studying the ultrafast dynamics of small molecules can serve as the first step in understanding the dynamics in larger chemically and biologically relevant molecules. To make direct comparisons with existing computational techniques, the photons used in pump-probe spectroscopy must make perturbative transitions between the electronic states of isolated small molecules. In this dissertation experimental investigations of ultrafast dynamics in electronic excitations of neutral ethylene and carbon dioxide are discussed. These experiments are performed using VUV/XUV femtosecond pulses as pump and probe.
To make photons with sufficient energy for single photon transitions, VUV and XUV light is generated by high harmonic generation (HHG) using a high pulse energy (≈30–40 mJ) Ti:sapphire femtosecond laser. Sufficient flux must be generated to enable splitting of the HHG light into pump and probe arms. The system produces >1010 photons per shot, corresponding to nearly 10 MW of peak power in the XUV. Using a high flux of high energy photons creates a unique set of challenges when designing a detector capable of performing pump-probe experiments. A velocity map imaging (VMI) detector has been designed to address these challenges, and has become a successful tool facilitating studies into molecular dynamics that were not possible before its implementation.
The emphasis on using high energy, single photon transitions allowed theoretical calculations to be directly compared to experimental yields for the first time. This comparison resolved a long standing issue in the excited state lifetime of ethylene, and provided a confirmation of the branching ratio between the two nonadiabatic relaxation pathways that return ethylene back to its ground state from the π*. The participation of the 3s Rydberg state has also been measured by collecting the time resolved photoelectron spectrum during the dynamics on ethylene’s π* excited state, confirming calculations predicting the effect of the 3s.
In carbon dioxide the first time resolved measurement in the lowest electronic excitation of carbon dioxide has been performed. A high kinetic energy release channel shows the signature of wavepacket dynamics within the excited state manifold. Deviation from the direct dissociation predicted for the pumped state provides experimental evidence confirming theoretical predictions of nonadiabatic transitions within the lowest lying electronically excited states.
|Advisor:||McCurdy, Clyde William|
|Commitee:||Belkacem, Ali, Ng, Cheuk-Yiu|
|School:||University of California, Davis|
|School Location:||United States -- California|
|Source:||DAI-B 77/08(E), Dissertation Abstracts International|
|Subjects:||Molecular chemistry, Quantum physics, Molecular physics|
|Keywords:||Dynamics, High harmonic generation, Molecule, Pump probe, Ultrafast, Velocity map imaging|
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