Mass analyzed threshold ionization of p-bromoaniline: heavy atom effects on electronic transition, ionization, and molecular vibration

• Published in: Chemical physics letters Vol. 356; no. 3; pp. 267 - 276
• Main Authors: Lin, J.L., Yang, S.C., Yu, Y.C., Tzeng, W.B.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 22.04.2002; Elsevier Science
• Subjects: Atomic and molecular physics; Autoionization, photoionization, and photodetachment; Exact sciences and technology; Molecular properties and interactions with photons; Photon interactions with molecules; Physics; Amines; Molecular structure; Bond angle; Time-of-flight method; Aniline derivatives; Organic bromine compounds; Experimental study; Bond lengths; Photoionization; Isotope effects; Transition energy; Vibrational modes; Benzenic compound; Vibronic transition; Electronic transition
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/S0009-2614(02)00329-9

We have recorded the vibrationally resolved spectra of p-bromoaniline in the S 1 and cationic ground state. The band origin of the S 1←S 0 electronic transition is found to be 32 590±1 cm −1 , whereas the adiabatic ionization energy is 62 308±5 cm −1 . Most of the active vibrations of p-bromoaniline in the S 1 and cationic ground states are related to the totally symmetric in-plane ring modes, as in aniline. Comparison among these new experimental data and those of aniline, p-fluoroaniline and p-chloroaniline offers a good understanding about the heavy atom effects on the electronic transition, ionization and molecular vibration. The experimental findings are well supported by the ab initio and density functional calculations.