title: Electronic spectra of 2- and 3-tolunitrile in the gas phase. I. A study of methyl group internal rotation via rovibronically resolved spectroscopy.
abstract: Rotationally resolved fluorescence excitation spectra of the origin bands in the S1 ← S0 transition of 2-tolunitrile (2TN) and 3-tolunitrile (3TN) have been recorded in the collision-free environment of a molecular beam. Analyses of these data provide the rotational constants of each molecule and the potential energy curves governing the internal rotation of the attached methyl groups in both electronic states. 2TN exhibits much larger barriers along this coordinate than 3TN. Interestingly, the electronic transition dipole moment in both molecules is markedly influenced by the position of the attached methyl group rather than the position of the cyano group; possible reasons for this intriguing behavior are discussed.
authors.affiliation: División de Ciencias e Ingenierías, Universidad de Guanajuato, León, Guanajuato 37150, México.
authors.forename: José Arturo
authors.initials: JA
authors.lastname: Ruiz-Santoyo
authors.affiliation: Institut für Physikalische Chemie, Heinrich-Heine-Universität, 40225 Düsseldorf, Deutschland.
authors.forename: Josefin
authors.initials: J
authors.lastname: Wilke
authors.affiliation: Institut für Physikalische Chemie, Heinrich-Heine-Universität, 40225 Düsseldorf, Deutschland.
authors.forename: Martin
authors.initials: M
authors.lastname: Wilke
authors.affiliation: Department of Chemistry, Winston-Salem State University, Winston-Salem, North Carolina 27110, USA.
authors.forename: John T
authors.initials: JT
authors.lastname: Yi
authors.affiliation: Department of Chemistry, University of Vermont, Burlington, Vermont 05405, USA.
authors.forename: David W
authors.initials: DW
authors.lastname: Pratt
authors.affiliation: Institut für Physikalische Chemie, Heinrich-Heine-Universität, 40225 Düsseldorf, Deutschland.
authors.forename: Michael
authors.initials: M
authors.lastname: Schmitt
authors.affiliation: División de Ciencias e Ingenierías, Universidad de Guanajuato, León, Guanajuato 37150, México.
authors.forename: Leonardo
authors.initials: L
authors.lastname: Álvarez-Valtierra