Abstract

Time-resolved photoelectron spectroscopy is applied to study the excited state dynamics of the DNA base adenine and its ribonucleoside adenosine in aqueous solution for pump and probe photon energies in the range between 4.66 eV and 5.21 eV. We follow the evolution of the prepared excited state on the potential energy surface and retrieve lifetimes of the S1 state under different excitation conditions.

Highlights

  • Interaction of ultraviolet light with DNA molecules may lead to photodamage and may cause development of cancer

  • We expect to observe excited state dynamics initiated by either UV pulse

  • Molecules are excited by 266 nm light and photoionized by 238 nm light

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Summary

Introduction

Interaction of ultraviolet light with DNA molecules may lead to photodamage and may cause development of cancer. Theoretical studies of isolated adenine (especially the 9H tautomer) in the gas phase identified several conical intersections (CIs) relevant for the excited state relaxation (pp*/np*, pp*/ps*, np*/S0, pp*/S0, ps*/S0)[3,4,5,6,7,8,23,24,25,26] (and references therein) These CIs are connected with geometrical changes of the molecule including an envelope puckering at the C2-atom (2E, pp*/S0), a pronounced out-of-plane distortion of the C6-atom and the amino group (1S6, np*/S0), stretch of the N9–H bond (ps*/S0) and/or C8–N9 bond breaking.

Experiment
Results and discussion
Time-dependent spectra of excited adenosine
Population dynamics of adenosine and adenine
81 Æ 7 76 Æ 5 64 Æ 2

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