The Threshold Photoelectron Spectrum of Fulvenone: A Reactive Ketene Derivative in Lignin Valorization.

ABSTRACT

Unveiling reaction mechanisms by isomer-selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C5 H4 =C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2-methoxy acetophenone. The high-resolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well-resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadiene moiety. The adiabatic ionization energy was determined to be 8.25±0.01 eV and is assigned to the X˜+2 A2 ← X˜1 A1 transition. A broad and featureless band arising at 9 eV is associated with the A˜+2 B1 ← X˜1 A1 excitation. A conical intersection is responsible for the ultrafast relaxation of the fulvenone cation from the A˜+ into the X˜+ state resulting in a featureless and lifetime broadened band. These insights will increase the detection capabilities for fulvenone and thereby help to elucidate reaction mechanisms in lignin catalytic pyrolysis.