Exploring quantum phenomena and vibrational control in σ* mediated photochemistry

Gareth M. Roberts, David J. Hadden, L. Therese Bergendahl, Andreas M. Wenge, Stephanie J. Harris, Tolga N. V. Karsili, Michael N. R. Ashfold*, Martin J. Paterson, Vasilios G. Stavros

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

49 Citations (Scopus)
282 Downloads (Pure)

Abstract

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* ...

Original languageEnglish
Pages (from-to)993-1001
Number of pages9
JournalChemical Science
Volume4
Issue number3
Early online date29 Nov 2012
DOIs
Publication statusPublished - 2013

Keywords

  • STATES
  • THIOPHENOL
  • SPECTROSCOPY
  • PHOTOELECTRON
  • UV PHOTODISSOCIATION
  • DYNAMICS
  • CONICAL INTERSECTIONS

Cite this

Roberts, G. M., Hadden, D. J., Bergendahl, L. T., Wenge, A. M., Harris, S. J., Karsili, T. N. V., Ashfold, M. N. R., Paterson, M. J., & Stavros, V. G. (2013). Exploring quantum phenomena and vibrational control in σ* mediated photochemistry. Chemical Science, 4(3), 993-1001. https://doi.org/10.1039/c2sc21865h