Cation States of Ethane: HEAT Calculations and Vibronic Simulations of the Photoelectron Spectrum of Ethane.

Abstract

High-accuracy ab initio calculations have been carried out on ethane and its radical cation. With the HEAT-345(Q) scheme, adiabatic ionization potentials of 11.52 and 11.57 eV are determined for the X̃ (2)Eg and à (2)A1g states, respectively, with an uncertainty of ±0.015 eV. Also considered in this report are linear and quadratic vibronic coupling involving both states. With this simple vibronic model, the photoelectron spectrum of ethane was simulated in the 11-15 eV region using linear and full quadratic Jahn-Teller coupling Hamiltonians, and with up to 70 billion direct product basis functions in a high-performance computing environment. Although the linear vibronic coupling model adequately reproduces the spectral envelope, the quadratic vibronic treatment results in much better agreement with the observed spectrum.