Photoexcitation of iodide ion-pyrimidine clusters above the electron detachment threshold: Intracluster electron transfer versus nucleobase-centred excitations

The Journal of Chemical Physics
Edward M MatthewsCaroline E H Dessent

Abstract

Laser photodissociation spectroscopy of the I-·thymine (I-·T) and I-·cytosine (I-·C) nucleobase clusters has been conducted for the first time across the regions above the electron detachment thresholds to explore the excited states and photodissociation channels. Although photodepletion is strong, only weak ionic photofragment signals are observed, indicating that the clusters decay predominantly by electron detachment. The photodepletion spectra of the I-·T and I-·C clusters display a prominent dipole-bound excited state (I) in the vicinity of the vertical detachment energy (∼4.0 eV). Like the previously studied I-·uracil (I-·U) cluster [W. L. Li et al., J. Chem. Phys. 145, 044319 (2016)], the I-·T cluster also displays a second excited state (II) centred at 4.8 eV, which we similarly assign to a π-π* nucleobase-localized transition. However, no distinct higher-energy absorption bands are evident in the spectra of the I-·C. Time-dependent density functional theory (TDDFT) calculations are presented, showing that while each of the I-·T and I-·U clusters displays a single dominant π-π* nucleobase-localized transition, the corresponding π-π* nucleobase transitions for I-·C are split across three separate weaker electronic excita...Continue Reading

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Jun 27, 2017·Physical Chemistry Chemical Physics : PCCP·Edward Matthews, Caroline E H Dessent

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Citations

Aug 3, 2019·International Journal of Molecular Sciences·Yi Zheng, Léon Sanche
Oct 24, 2019·The Journal of Chemical Physics·Alice KuninDaniel M Neumark
Jul 16, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Kelechi O UleanyaCaroline E H Dessent
Sep 12, 2020·Physical Review Letters·Do Hyung KangSang Kyu Kim
Aug 17, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Edward MatthewsCaroline E H Dessent
Nov 25, 2020·Physical Chemistry Chemical Physics : PCCP·Jennifer A NobleChristophe Jouvet
Aug 4, 2021·The Journal of Physical Chemistry. a·Natalie G K WongCaroline E H Dessent
Aug 8, 2021·International Journal of Molecular Sciences·Yingxia GaoLéon Sanche
May 14, 2020·The Journal of Physical Chemistry Letters·Hanhui ZhangXue-Bin Wang
Oct 3, 2018·The Journal of Physical Chemistry Letters·Edward Matthews, Caroline E H Dessent
May 18, 2019·The Journal of Physical Chemistry Letters·Yanfang DongLéon Sanche

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