Abstract
AbstractThe ZEKE photoelectron spectrum of methyl formate in a supersonic jet was recorded using multibunch VUV synchrotron radiation. The adiabatic ionisation potential is determined to 87 390 cm−1 (10.835 eV). Three yet unobserved normal modes of the electronic ground state (ν10, ν11, and ν12) and the progression of a mode previously assigned to ν4 are observed. Ab initio calculations reveal a large Duschinsky rotation upon ionisation of three modes implying that the ν4 progression corresponds to an OCO‐antisymmetrical stretch motion. The finer vibrational structure observed on the electronic ground state above 1500 cm−1 is considerably perturbed due to the anharmonicity of the potential surface.
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