Electronic structure of adenine and thymine base pairs studied by femtosecond electron-ion coincidence spectroscopy
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- Electronic structure of adenine and thymine base pairs studied by femtosecond electron-ion coincidence spectroscopy
- Gador, Niklas; Samoylova, Elena; Smith, Valoris Reid; Stolow, Albert; Rayner, David M.; Radloff, Wolfgang; Hertel, Ingolf Volker; Schultz, Thomas
- RESOLVED PHOTOELECTRON-SPECTROSCOPY; NUCLEIC-ACID BASES; ULTRAFAST INTERNAL-CONVERSION; PROTON-TRANSFER PROCESSES; EXCITED-STATE DYNAMICS; ISOLATED DNA BASES; RNA BASES; MOLECULAR-DYNAMICS; LASER SPECTROSCOPY; AB-INITIO
- Issue Date
- AMER CHEMICAL SOC
- JOURNAL OF PHYSICAL CHEMISTRY A, v.111, no.46, pp.11743 - 11749
- Femtosecond pump - probe spectroscopy was combined with photoelectron - photoion coincidence detection to investigate the electronic structure and dynamics of isolated adenine (A) and thymine (T) dimers and the adenine-thymine (AT) base pair. The photoelectron spectra show that ππ* and ππ* states are only weakly perturbed in the hydrogen-bound dimers as compared to the monomers. For cationic base pairs with internal energies greater than 1 eV, we observed considerable cluster fragmentation into protonated monomers. This process selectively removed signals from the ππ* → n-1 ionization channel in all dimers. The photoelectron spectra are compared to time-resolved mass spectra and confirm the assignment of short-lived ππ* and nπ* populations in the adenine, thymine, and mixed AT dimers.
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