Excited states of aniline by photoabsorption spectroscopy in the 30 000-90 000 cm-1 region using synchrotron radiation

The photoabsorption spectrum of aniline (C6H5NH2) in gas phase in the 30 000-90 000 cm(-1) (3.7-11.2 eV) region is recorded at resolution limit of 0.008 eV using synchrotron radiation source for the first time to comprehend the nature of the excited valence and Rydberg states. The first half of the energy interval constitutes the richly structured valence transitions from the ground to excited states up to the first ionization potential (IP) at 8.02 eV. The spectrum in the second half consists of vibrational features up to second IP (9.12 eV) and structureless broad continuum up to the third IP (10.78 eV). The electronic states are assigned mainly to the singlets belonging to pi -> pi* transitions. A few weak initial members of Rydberg states arising from pi -> 4s, np or nd transitions are also identified. Observed vibrational features are assigned to transitions from the ground state A' to the excited states 1A '', 3A', 5A,'' 6A', and 10A '' in C-s symmetry. Time dependent density functional theory (TDDFT) calculations at B3LYP level of theory are employed to obtain the vertical excitation energies and the symmetries of the excited states in equilibrium configuration. The computed values of the transition energies agree fairly well with the experimental data. Further the calculated oscillator strengths are used to substantiate the assignments of the bands. The work provides a comprehensive picture of the vacuum ultraviolet photoabsorption spectrum of aniline up to its third ionization limit. (C) 2013 AIP Publishing LLC.