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Title: Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission

Abstract

We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ~1.7 eV, values that are lower than the RCB of the uncomplexed PtCl 6 2- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl 6 2-∙thymine and PtCl 6 2-∙adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN) 4 2-∙nucleobase complexes. The observation of delayed electron emission bands in the PtCl6 2-∙nucleobase spectra obtained in this work, as for the previously studied Pt(CN) 4 2-∙nucleobase complexes, is attributed to onephoton excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover,more » the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. Here, this strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a timescale long enough to allow autodetachment.« less

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [1]
  1. Univ. of York (United Kingdom)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1243269
Alternate Identifier(s):
OSTI ID: 1225769
Report Number(s):
PNNL-SA-113578
Journal ID: ISSN 0021-9606; JCPSA6; 48585; KC0301050
Grant/Contract Number:  
AC05-76RL01830; 208589-BIOIONS; KC0301050-16248
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 18; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory; Isomerism; Nucleobases; Autoionization; Coulomb barrier; Ions and properties; Photoelectron spectroscopy; Basis sets; Thymine; Gas phase; Density functional theory

Citation Formats

Sen, Ananya, Matthews, Edward M., Hou, Gao-Lei, Wang, Xue-Bin, and Dessent, Caroline E. H. Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission. United States: N. p., 2015. Web. doi:10.1063/1.4935171.
Sen, Ananya, Matthews, Edward M., Hou, Gao-Lei, Wang, Xue-Bin, & Dessent, Caroline E. H. Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission. United States. https://doi.org/10.1063/1.4935171
Sen, Ananya, Matthews, Edward M., Hou, Gao-Lei, Wang, Xue-Bin, and Dessent, Caroline E. H. Wed . "Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission". United States. https://doi.org/10.1063/1.4935171. https://www.osti.gov/servlets/purl/1243269.
@article{osti_1243269,
title = {Photoelectron spectroscopy of hexachloroplatinate-nucleobase complexes: Nucleobase excited state decay observed via delayed electron emission},
author = {Sen, Ananya and Matthews, Edward M. and Hou, Gao-Lei and Wang, Xue-Bin and Dessent, Caroline E. H.},
abstractNote = {We report low-temperature photoelectron spectra of isolated gas-phase complexes of the hexachloroplatinate dianion bound to the nucleobases uracil, thymine, cytosine and adenine. The spectra display well-resolved, distinct peaks that are consistent with complexes where the hexachloroplatinate dianion is largely intact. Adiabatic electron detachment energies for the hexachloroplatinate-nucleobase complexes are measured as 2.26-2.36 eV. The magnitudes of the repulsive Coulomb barriers (RCBs) of the complexes are all ~1.7 eV, values that are lower than the RCB of the uncomplexed PtCl62- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photoelectron spectra of the four clusters. The 266 nm spectra of the PtCl62-∙thymine and PtCl62-∙adenine complexes also display very prominent delayed electron emission bands. These results mirror recent results on the related Pt(CN)42-∙nucleobase complexes. The observation of delayed electron emission bands in the PtCl6 2-∙nucleobase spectra obtained in this work, as for the previously studied Pt(CN)42-∙nucleobase complexes, is attributed to onephoton excitation of nucleobase-centred excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment. Moreover, the selective, strong excitation of the delayed emission bands in the 266 nm spectra is linked to fundamental differences in the individual nucleobase photophysics at this excitation energy. Here, this strongly supports our previous suggestion that the dianion within these clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase decays over a timescale long enough to allow autodetachment.},
doi = {10.1063/1.4935171},
url = {https://www.osti.gov/biblio/1243269}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 18,
volume = 143,
place = {United States},
year = {2015},
month = {11}
}

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