Probing the vibrational spectroscopy of the deprotonated thymine radical by photodetachment and state-selective autodetachment photoelectron spectroscopy via dipole-bound states.

ABSTRACT: Deprotonated thymine can exist in two different forms, depending on which of its two N sites is deprotonated: N1[T-H]- or N3[T-H]-. Here we report a photodetachment study of the N1[T-H]- isomer cooled in a cryogenic ion trap and the observation of an excited dipole-bound state. Eighteen vibrational levels of the dipole-bound state are observed, and its vibrational ground state is found to be 238 ± 5 cm-1 below the detachment threshold of N1[T-H]-. The electron affinity of the deprotonated thymine radical (N1[T-H]?) is measured accurately to be 26?322 ± 5 cm-1 (3.2635 ± 0.0006 eV). By tuning the detachment laser to the sixteen vibrational levels of the dipole-bound state that are above the detachment threshold, highly non-Franck-Condon resonant-enhanced photoelectron spectra are obtained due to state- and mode-selective vibrational autodetachment. Much richer vibrational information is obtained for the deprotonated thymine radical from the photodetachment and resonant-enhanced photoelectron spectroscopy. Eleven fundamental vibrational frequencies in the low-frequency regime are obtained for the N1[T-H]? radical, including the two lowest-frequency internal rotational modes of the methyl group at 70 ± 8 cm-1 and 92 ± 5 cm-1.

SUBMITTER: Huang DL 

PROVIDER: S-EPMC5657408 | biostudies-literature | 2015 May

REPOSITORIES: biostudies-literature