Multi-faceted spectroscopic study of the structural changes associated with electronic excitation of methyl anthranilate

Blodgett, Karl N.

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https://hdl.handle.net/2142/104338 Copy

Description

Title

Multi-faceted spectroscopic study of the structural changes associated with electronic excitation of methyl anthranilate

Author(s)

Blodgett, Karl N.

Contributor(s)

• Zwier, Timothy S.
• Sibert, Edwin
• Fischer, Joshua L.
• Sun, Dewei

Issue Date

2019-06-17

Keyword(s)

Vibrational structure/frequencies

Abstract

Methyl anthranilate (MA) is the methyl ester of anthranilic acid. We present the jet-cooled Laser Induced Fluorescence (LIF) UV excitation spectrum, ground (S$_{0}$) and excited state (S$_{1}$) Fluorescence Dip Infrared (FDIR) spectra, IR-UV Holeburning (IR-UV HB) spectra, and Dispersed Fluorescence (DFL) spectra of the MA monomer and MA-H$_{2}$O complex. MA is a close analog of salicylic acid, a well-studied molecule thought to undergo keto-enol tautomerism involving excited state H-atom transfer. In the MA monomer, the C6 ring formed by the H$_{a}$NH$_{b}$ $^{...}$ O=C hydrogen bond in the ground state undergoes an unusual increase in hydrogen bond strength following electronic excitation to the S$_{1}$ state. This is evident in the spectroscopy in several ways. The LIF excitation and DFL spectra both show long progressions in several modes involving motion of the NH$_{2}$ and COOMe groups relative to one another. Furthermore, the coupled NH$_{2}$ symmetric and asymmetric stretch fundamentals appear to uncouple upon UV excitation, giving rise to a broadened (8 cm$^{-1}$ FWHM), nominally “free” N-H$_{a}$ stretch at 3458 cm$^{-1}$ and an N-H$_{b}$ stretch shifted all the way down to \~{}2900 cm$^{-1}$. FDIR spectra collected in the mid-IR frequency range show the change in hydrogen bond strength from the perspective of the C=O acceptor group, where the stretch fundamental is shifted down from its S$_{0}$ position at 1721 cm$^{-1}$ to 1637 cm$^{-1}$ in S$_{1}$. Calculations at the B3LYP-D3/def2TZVP level of theory in large measure capture these frequency shifts and give insight into likely explanations for such drastic changes. Similar behavior is observed in the MA-H$_{2}$O complex, although the extent of the hydrogen bond strengthening in the S$_{1}$ state is modulated by the HOH interactions with both the NH$_{2}$ and C=O groups.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/104338

DOI

https://doi.org/10.15278/isms.2019.ML07

Copyright and License Information

Copyright 2019 Karl N. Blodgett

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