High harmonic generation and molecular orbital tomography in multielectron systems: Beyond the single active electron approximation

Abstract

It was recently shown that the highest molecular orbital of N2 could be reconstructed from a series of high harmonic measurements. Existing theories of high harmonic generation and orbital tomographic imaging are based on the single active electron approximation that ignores essential quantum mechanical properties such as the indistinguishability of identical particles and the Pauli exclusion principle. We show that, when fully antisymmetrized multielectron wave functions and electronic relaxation in the cation are considered, molecular orbital tomography records the image of the Dyson orbital plus exchange contributions from inner shells. The mixing of contributions from more than one molecular orbital gives access to additional wave function information. By utilizing the exchange term, harmonic emission from a closed-shell 4-electron system can be interpreted as a complete Hartree-Fock wave function. © 2006 The American Physical Society.