Berlin 2014 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 19: Femtosecond Spectroscopy 2
MO 19.5: Vortrag
Donnerstag, 20. März 2014, 17:30–17:45, BEBEL HS213
Photodynamics and structure of a 1-methylthymine self-pair mediated by a silver trimer — •Yevgeniy Nosenko1, Christoph Riehn1, Gereon Niedner-Schatteburg1, and Wim Klopper2 — 1TU Kaiserslautern, FB Chemie und Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 52, 67663 Kaiserslautern — 2Karlsruher Institut für Technologie (KIT), Institut für Physikalische Chemie, Fritz-Haber-Weg 2, 76131 Karlsruhe
A cationic self-pair of deprotonated 1-methylthymine (1MT-H) mediated by a unique linear arrangement of three silver ions, [(Ag)3(1MT-H)2]+, was obtained by electrospray ionization from a methanolic solution and investigated in an ion trap at ca. 305 K by laser spectroscopy. Structure and photodynamics of the MBP was explored using IR multiple photon dissociation, femtosecond transient photo-fragmentation (PF) and ab initio calculations at the CC2 level of theory. Two time constants, 0.16(12) ps and 1.0(3) ps, are obtained from fitting of the 283 nm pump - 700 nm probe transient PF spectrum. The picosecond component is several times faster than in the thymine monomer, indicating an acceleration of the electronic relaxation induced by the metal coordination. Electronic relaxation pathways via LMCT or metal centered singlet excited states are discussed.