Non-adiabatic dynamics involving (1)pi sigma* or (1)n sigma* excited electronic states play a key role in the photochemistry of numerous heteroatom containing aromatic (bio-) molecules. In this contribution, we investigate more exotic phenomena involved in sigma* mediated dynamics, namely: (i) the role of purely quantum mechanical behavior; and (ii) manipulating non-adiabatic photochemistry through conical intersections (CIs) with 'vibration-specific control'. This is achieved by investigating S-CH3 bond fission via a (1)n sigma* potential energy surface (PES) in thioanisole (C6H5SCH3). Using a combination of time- and frequency-resolved velocity map ion imaging techniques, together with ab initio calculations, we demonstrate that excitation to the (1)pi pi* ...
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