Excimer

About: Excimer is a research topic. Over the lifetime, 3725 publications have been published within this topic receiving 75104 citations.

The role of adenine excimers in the photophysics of oligonucleotides.

Abstract: Energies and structures of different arrangements of the stacked adenine homodimer have been computed at the ab initio CASPT2 level of theory in isolation and in an aqueous environment. Adenine dimers are shown to form excimer singlet states with different degrees of stacking and interaction. A model for a 2-fold decay dynamics of adenine oligomers can be supported in which, after initial excitation in the middle UV range, unstacked or slightly stacked pairs of nucleobases will relax by an ultrafast internal conversion to the ground state, localizing the excitation in the monomer and through the corresponding conical intersection with the ground state. On the other hand, long-lifetime intrastrand stacked excimer singlet states will be formed in different conformations, including neutral and charge transfer dimers, which originate the red-shifted emission observed in the oligonucleotide chains and that will evolve toward the same monomer decay channel after surmounting an energy barrier. By computing the transient absorption spectra for the different structures considered and their relative stability in vacuo and in water, it is concluded that in the adenine homodimers the maximum-overlap face-to-face orientations are the most stable excimer conformations observed in experiment.

Excimer formation and evolution of excited state properties in discrete dimeric stacking of an anthracene derivative: a computational investigation

Abstract: Herein, density functional theory (DFT) computations were performed to investigate the discrete dimer of a mono-substituted anthracene derivative (2-TA-AN), which exhibited highly efficient pure excimer fluorescence in its crystal form. As a more practical model, its geometry, potential energy curve and excited state property were systematically calculated to better understand the excimer formation process and photophysical properties. The compressed excimer geometry is responsible for the highly efficient excimer emission, arising from the enhanced rigidity that greatly suppresses its non-radiative vibrations. Potential energy curves along three directions reveal the non-uniqueness of excimer formation along the long axis of anthracene, which is in a good agreement with the experimental findings. Upon decreasing the displacement, the intermonomer charge-transfer (CT) component gradually increased towards an approximately equivalent hybridization with the locally-emissive (LE) state of the monomer during the formation of the excimer. The excimer emission wavelength versus intermonomer CT content shows a similar trend along the three directions, revealing a turning point related to the essential transition of the excited state properties from the LE of the monomer to the HLCT of the excimer. The present results will contribute to the better understanding of the structure-property relationships in excimer formation and photophysical properties.

Interaction Effects on Lifetimes of Atomic Excitations

Abstract: The apparent lifetime of an excited atom in a p state is investigated when another atom, in an s ground state, is present. The dependence of the lifetime on the distance RAB between the two atoms is obtained. It is found that the results for a p0 state differ somewhat from those for the p±1 states. (The axis of quantization is taken as the line joining the two atoms.)