|Title||Intrinsic photophysics of nitrophenolate ions studied by cryogenic ion spectroscopy|
|Publication Type||Journal Article|
|Year of Publication||2018|
|Authors||Dodson, LG, Zagorec-Marks, W, Xu, S, Smith, JET, J. Weber, M|
|Journal||Physical Chemistry Chemical Physics|
|Pagination||28535 - 28543|
The intrinsic photophysics of nitrophenolate isomers (meta, para, and ortho) was studied at low temperature using photodissociation mass spectrometry in a cryogenic ion trap instrument. Each isomer has distinct photophysics that affects the excited state lifetimes, as observed experimentally in their spectroscopic linewidths. Visible-light-induced excitation of m-nitrophenolate gives rise to well-resolved vibronic features in the spectrum of the S1 state. The para and ortho isomers have broad spectra – even at cryogenic temperatures – due to their shorter excited state lifetimes and spectral congestion. We present computational evidence for mixing of the first and second excited states of o-nitrophenolate, leading to significant additional broadening in the experimental spectrum.