Spectral jumps

Figure Cl.5.8. Spectral jumping of a single molecule of terrylene in polyethylene at 1.5 K. The upper trace displays fluorescence excitation spectra of tire same single molecule taken over two different 20 s time intervals, showing tire same molecule absorbing at two distinctly different frequencies. The lower panel plots tire peak frequency in tire fluorescence excitation spectmm as a function of time over a 40 min trajectory. The molecule undergoes discrete jumps among four (briefly five) different resonant frequencies during tliis time period. Arrows represent scans during which tire molecule had jumped entirely outside tire 10 GHz scan window. Adapted from...

Once a single molecule line has been isolated with sufficient signal/noise ratio in a fluorescence excitation spectrum (Chapter 1.1), it may or may not exhibit instability due to spectral jumps [40]. Large irreversible jumps move the molecular line outside... 

Figure 2. Example of spectral jumps of a single pentacene molecule in p-terphenyl, interrupting emission during two scans of the laser (reproduced from Ref 40).

In 1991, Basche and Moerner included perylene in polyethylene [71]. The small and rigid perylene molecule has good emission and triplet properties, but absorbs in a difficult spectral region, around 445 nm. Because the spectral jumps we discuss here are mainly consequences of matrix dynamics, we must shortly discuss sample preparation. The samples of [71] were made from low-density polyethylene (crystallinity 25%), doped at low concentration with perylene, and were quickly quenched from the melt to liquid nitrogen temperature to reduce light scattering. The thin films thus obtained were 10 to 20 pm thick. The polymer structure is thus expected to be dominantly amorphous. 

---