Quantum mechanical study of the attosecond nonlinear Fourier transform spectroscopy of carbon dioxide

TL;DR

This paper presents a quantum mechanical framework for analyzing attosecond nonlinear Fourier transform spectroscopy of CO2, enabling detailed interpretation of experimental spectra and prediction of spectral features for diatomic and triatomic molecules.

Contribution

It introduces a quantum mechanical model based on perturbation theory and ab initio calculations to interpret NFT spectra, which was not previously available.

Findings

The model captures key features of experimental NFT spectra of CO2.

Analytic expressions help assign spectral lines to electronic states.

Framework predicts spectra for di- and triatomic molecules semi-quantitatively.

Abstract

Attosecond nonlinear Fourier transform (NFT) pump probe spectroscopy is an experimental technique which allows investigation of the electronic excitation, ionization, and unimolecular dissociation processes. The NFT spectroscopy utilizes ultrafast multiphoton ionization in the extreme ultraviolet spectral range and detects the dissociation products of the unstable ionized species. In this paper, a quantum mechanical description of NFT spectra is suggested, which is based on the second order perturbation theory in molecule-light interaction and the high level ab initio calculations of CO2 and CO2+ in the Franck-Condon zone. The calculations capture the characteristic features of the available experimental NFT spectra of CO2. Approximate analytic expressions are derived and used to assign the calculated spectra in terms of participating electronic states and harmonic photon frequencies. The developed approach provides a convenient framework within which the origin and the significance of near harmonic and non-harmonic NFT spectral lines can be analyzed. The framework is scalable and the spectra of di- and triatomic species as well as the dependences on the control parameters can by predicted semi-quantitatively.