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Title: Vibrationally-resolved Photoelectron Spectroscopy of the Model GFP Chromophore Anion Revealing the Photoexcited S-1 State being both Vertically and Adiabatically Bound against the Photodetached D-0 Continuum

Abstract

The first excited state of the model green fluorescence protein (GFP) chromophore anion (S1) and its energy level against the electron-detached neutral radical, D0 state are crucial in determining the photophysics and the photo-induced dynamics of GFP. Extensive experimental and theoretical studies, particularly several very recent gas phase investigations concluded that S1 is a bound state in the Franck-Condon vertical region with respect to D0. However, what remains unknown and challenging is if S1 is bound adiabatically, primarily due to lack of accurate experimental measurements, as well as due to close proximity in energy for these two states that even sophisticated high-level ab initio calculations can’t reliably predict. Here, we report a negative ion photoelectron spectroscopy study on the model GFP chromophore anion, the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI–). Despite the considerable size and low symmetry of the molecule, well resolved vibrational structures were obtained with the 0–0 transition being the most intense peak. The adiabatic (ADE) and vertical detachment energy (VDE) therefore are determined, both to be 2.73 ± 0.01 eV, indicating the detached D0 state is 0.16 eV higher in energy than the photon excited S1 state. The accurate ADE and VDE values and the well-resolved photoelectron spectra reportedmore » here provide much needed, robust benchmarks for future theoretical investigations.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1172442
Report Number(s):
PNNL-SA-102602
44678; KC0301020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry Letters, 5(12):2155-2159
Additional Journal Information:
Journal Name: Journal of Physical Chemistry Letters, 5(12):2155-2159
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Deng, Shihu, Kong, Xiangyu, Zhang, GuanXin, Yang, Yan, Zheng, Weijun, Sun, Zhenrong, Zhang, De-Qing, and Wang, Xue B. Vibrationally-resolved Photoelectron Spectroscopy of the Model GFP Chromophore Anion Revealing the Photoexcited S-1 State being both Vertically and Adiabatically Bound against the Photodetached D-0 Continuum. United States: N. p., 2014. Web. doi:10.1021/jz500869b.
Deng, Shihu, Kong, Xiangyu, Zhang, GuanXin, Yang, Yan, Zheng, Weijun, Sun, Zhenrong, Zhang, De-Qing, & Wang, Xue B. Vibrationally-resolved Photoelectron Spectroscopy of the Model GFP Chromophore Anion Revealing the Photoexcited S-1 State being both Vertically and Adiabatically Bound against the Photodetached D-0 Continuum. United States. https://doi.org/10.1021/jz500869b
Deng, Shihu, Kong, Xiangyu, Zhang, GuanXin, Yang, Yan, Zheng, Weijun, Sun, Zhenrong, Zhang, De-Qing, and Wang, Xue B. 2014. "Vibrationally-resolved Photoelectron Spectroscopy of the Model GFP Chromophore Anion Revealing the Photoexcited S-1 State being both Vertically and Adiabatically Bound against the Photodetached D-0 Continuum". United States. https://doi.org/10.1021/jz500869b.
@article{osti_1172442,
title = {Vibrationally-resolved Photoelectron Spectroscopy of the Model GFP Chromophore Anion Revealing the Photoexcited S-1 State being both Vertically and Adiabatically Bound against the Photodetached D-0 Continuum},
author = {Deng, Shihu and Kong, Xiangyu and Zhang, GuanXin and Yang, Yan and Zheng, Weijun and Sun, Zhenrong and Zhang, De-Qing and Wang, Xue B.},
abstractNote = {The first excited state of the model green fluorescence protein (GFP) chromophore anion (S1) and its energy level against the electron-detached neutral radical, D0 state are crucial in determining the photophysics and the photo-induced dynamics of GFP. Extensive experimental and theoretical studies, particularly several very recent gas phase investigations concluded that S1 is a bound state in the Franck-Condon vertical region with respect to D0. However, what remains unknown and challenging is if S1 is bound adiabatically, primarily due to lack of accurate experimental measurements, as well as due to close proximity in energy for these two states that even sophisticated high-level ab initio calculations can’t reliably predict. Here, we report a negative ion photoelectron spectroscopy study on the model GFP chromophore anion, the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI–). Despite the considerable size and low symmetry of the molecule, well resolved vibrational structures were obtained with the 0–0 transition being the most intense peak. The adiabatic (ADE) and vertical detachment energy (VDE) therefore are determined, both to be 2.73 ± 0.01 eV, indicating the detached D0 state is 0.16 eV higher in energy than the photon excited S1 state. The accurate ADE and VDE values and the well-resolved photoelectron spectra reported here provide much needed, robust benchmarks for future theoretical investigations.},
doi = {10.1021/jz500869b},
url = {https://www.osti.gov/biblio/1172442}, journal = {Journal of Physical Chemistry Letters, 5(12):2155-2159},
number = ,
volume = ,
place = {United States},
year = {Thu Jun 19 00:00:00 EDT 2014},
month = {Thu Jun 19 00:00:00 EDT 2014}
}