Document Type

Article

Publication Date

7-28-2017

Abstract

An extended Jahn-Teller Hamiltonian is presented for the case where the (slow) nuclear motion extends far from the symmetry point and may be described approximately as motion on a sphere. Rather than the traditional power series expansion in the displacement from the C3v symmetry point, an expansion in the spherical harmonics is employed. Application is made to the vibrational Jahn-Teller effect in CH3XH, with X = S, O, where the equilibrium CXH angles are 83° and 72°, respectively. In addition to the symmetry-required conical intersection (CI) at the C3v symmetry point, ab initio calculations reveal sets of six symmetry-allowed vibrational CIs in each molecule. The CIs for each molecule are arranged differently in the large-amplitude space, and that difference is reflected in the infrared spectra. The CIs in CH3SH are found in both eclipsed and staggered geometries, whereas those for CH3OH are found only in the eclipsed geometry near the torsional saddle point. This difference between the two molecules is reflected in the respective high-resolution spectra in the CH stretch fundamental region.

Comments

© 2017 the authors. Original published version available at http://doi.org/10.1063/1.4994699.

Dawadi, M., Thapaliya, B., Perry, R. An Extended Jahn-Teller Hamiltonian for Large-Amplitude Motion: Application To Vibrational Conical Intersections in CH3SH and CH3OH. Journal of Chemical Physics 2017, vol. 147, article no. 44306.

Publication Title

Journal of Chemical Physics

DOI

10.1063/1.4994699

Included in

Chemistry Commons

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.