Anharmonic Vibrational Dynamics of DNA Oligomers

Combining two-color infared pump-probe spectroscopy and anharmonic force field calculations we characterize the anharmonic coupling patterns between fingerprint modes and the hydrogen-bonded symmetric NH$_2$ stretching vibration in adenine-thymine dA$_{20}$-dT$_{20}$ DNA oligomers. Specifically, it is shown that the anharmonic coupling between the NH$_2$ bending and the CO stretching vibration, both absorbing around 1665 cm-1, can be used to assign the NH$_2$ fundamental transition at 3215 cm-1 despite the broad background absorption of water.