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Near-threshold electron transfer in anion-nucleobase clusters: Does the identity of the anion matter?

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JournalMolecular Physics
DateAccepted/In press - 11 Mar 2019
DateE-pub ahead of print (current) - 24 Mar 2019
Number of pages10
Early online date24/03/19
Original languageEnglish


Laser dissociation spectroscopy of I ·adenine (I ·A) and H 2 PO 3 ·adenine (H 2 PO 3 ·A) has been utilised for the first time to explore how the anion identity impacts on the excited states. Despite strong photodepletion, ionic photofragmentation is weak for both clusters, revealing that they decay predominantly by electron detachment. The spectra of I ·A display a prominent dipole-bound excited state in the region of the detachment energy which relaxes to produce deprotonated adenine. In contrast, near-threshold photoexcitation of H 2 PO 3 ·A does not access a dipole-bound state, but instead displays photofragmentation properties associated with ultrafast decay of an adenine-localised π→π* transition. Notably, the experimental electron detachment onset of H 2 PO 3 ·A is around 4.7 eV, which is substantially lower than the expected detachment energy of an ion-dipole complex. The low value for H 2 PO 3 ·A can be traced to initial ionisation of the adenine followed by significant geometric rearrangement on the neutral surface. We conclude that these dynamics quench access to a dipole-bound excited state for H 2 PO 3 ·A and subsequent electron transfer. H 2 PO 3 ·A represents an important new example of an ionic cluster where ionisation occurs from the neutral cluster component and where photodetachment initiates intra-molecular hydrogen atom transfer.

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© 2019 Informa UK Limited, trading as Taylor & Francis Group. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

    Research areas

  • electron attachment, electronic excitation, gas phase, Nucleobase, photodissociation


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