Coupling of a Jahn–Teller pseudorotation with a hindered internal rotation in an isolated molecule: 9-hydroxytriptycene

Abstract

Experimental investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part II. Vibrational analysis of the A ̃ E 3 ″ 2 -X ̃ E 2 ″ 2 electronic transition J. Chem. Phys. 128, 084311 (2008) The Jahn-Teller effect in the lower electronic states of benzene cation. III. The ground-state vibrations of C 6 H 6 + and C 6 D 6 + J. Chem. Phys. 120, 8587 (2004) The irregular vibronic structure in the S 1 ←S 0 resonant two-photon ionization ͑R2PI͒ spectrum of supersonically cooled triptycene is a result of a classic E e Jahn-Teller effect ͓A. Furlan et al., J. Chem. Phys. 96, 7306 ͑1992͔͒. This is well characterized and can be used as an effective probe of intramolecular perturbations. Here we examine the S 1 ←S 0 R2PI spectrum of 9-hydroxytriptycene and the fluorescence from various excited state vibronic levels. In this system the pseudorotation of the Jahn-Teller vibration is strongly coupled to the torsional motion of the bridgehead hydroxy group. This torsional motion results in a tunneling splitting in both the ground and excited states. The population of the upper level in the ground electronic state results in additional vibronic transitions becoming symmetry allowed in the R2PI spectrum that are forbidden in the bare triptycene molecule. The assignment of the R2PI and fluorescence spectra allows the potential energy surfaces of these vibrational modes to be accurately quantified. The full C 3v vibronic point group must be used to interpret the spectra. The time scale of the internal rotation of the-OH group and the butterfly flapping of the Jahn-Teller pseudorotation are of similar magnitude. The tunneling between the nine minima on the three dimensional potential energy surface is such that the JahnTeller pseudorotation occurs in concert with the-OH internal rotation. The Berry phase that is acquired during this motion is discussed. The simple physical picture emerges of the angle between two of the three benzene moieties opening in three equivalent ways in the S 1 electronic state. This geometry follows the position of the hydroxy group, which preferentially orients itself to point between these two rings.

Reactive Pathways in the Chlorobenzene–Ammonia Dimer Cation Radical: New Insights from Experiment and Theory

“…The data supported a π-type structure for the complex, which, however, was determined in model calculations to be extremely floppy. In the ensuing years, ionization based methods have been extensively applied to the study of molecular complexes. − …”