Vibronic Coupling through the Continuum in the e + CO2 System

Article

Vibronic Coupling through the Continuum in the e + CO2 System

Jan Dvořák; Miloš Ranković; Karel Houfek; Pamir Nag; Roman Čurík; Juraj Fedor; Martin Čížek

Phys. Rev. Lett. 129(1) (2022)

Abstract

We report two-dimensional electron energy-loss spectra of CO2. The high-resolution experiment reveals a counterintuitive fine structure at energy losses where CO2 states form a vibrational pseudocontinuum. Guided by the symmetry of the system, we constructed a four-dimensional nonlocal model for the vibronic dynamics involving two shape resonances (forming a Renner-Teller Πu doublet at the equilibrium geometry) coupled to a virtual Σg+ state. The model elucidates the extremely non-Born-Oppenheimer dynamics of the coupled nuclear motion and explains the origin of the observed structures. It is a prototype of the vibronic coupling of metastable states in continuum.

Institute authors

Supported by

GACR 19-20524S — Electron-driven atomic and molecular processes - development of ab initio methods
GAUK552120 — Rezonanční srážky v nelokální teorii: konstrukce modelů a jejich použití na polyatomika

BibTeX

@article{UTF871,
  author        = {Jan Dvořák and Miloš Ranković and Karel Houfek and Pamir Nag and Roman Čurík and Juraj Fedor and Martin Čížek},
  title         = {{Vibronic Coupling through the Continuum in the e + CO2 System}},
  journal       = {Phys. Rev. Lett.},
  volume        = {129},
  number        = {1},
  year          = {2022},
  doi           = {10.1103/PhysRevLett.129.013401},
}