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Keywords:

  • carbenes;
  • diazirine;
  • laser spectroscopy;
  • molecular dynamics;
  • photodissociation
Thumbnail image of graphical abstract

Lights, spectrometer, action: Crucial information about the detailed shape of the potential-energy surface in the vicinity of the transition state is obtained from the Fano resonances in the photodissociation cross-section of diazirine in the S1 state. The excitation along the asymmetric C[BOND]N stretching mode accelerates the ring-opening reaction, suggesting that two C[BOND]N bonds of the excited diazirine break in a stepwise manner (see scheme).