ABSTRACT

Damage to the genome by UV light has fueled interest in excited

electronic states of DNA for over 50 years. DNA is also a fascinating

model system for understanding how two widespread supramole-

cular self-assembly motifs, π -π stacking and hydrogen bonding,

influence exciton dynamics in multichromophoric assemblies. The

importance of minimizing photochemical damage has endowed

DNA with remarkable photophysical properties that could inspire

new approaches to controlling exciton and charge transport in

nanomaterials. Although most excitations in single DNA bases decay

nonradiatively in hundreds of femtoseconds, much longer-lived

excited states are observed in femtosecond transient absorption

experiments on single-and double-stranded DNAs. Experiments on

single-stranded nucleic acids isolate effects due to base stacking.

Base stacking is shown to be of paramount importance for the

slow, nonradiative decay channels. This chapter provides a detailed

discussion of the femtosecond transient absorption technique with

emphasis on considerations relevant to studies of DNA excited-

state dynamics. A rate equation analysis of transient absorption

signal strengths is presented and used to reach conclusions about

excited states from experiments on single-stranded adenine homo-

oligonucleotides.