Intrinsic photophysics of nitrophenolate ions studied by cryogenic ion spectroscopy
Leah G Dodson1, Wyatt Zagorec-Marks, Shuang Xu
1JILA and NIST, University of Colorado, 0440 UCB, Boulder, CO 80309-0440, USA.
Abstract:
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.
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