Coupled Cluster and Time-Dependent Density Functional Theory Description of Inner Shell Photoabsorption Cross Sections of Molecules.

Abstract

Near K-edge photoabsorption cross section spectra of a number of molecules, namely, water, ammonia, acetone, acetaldehyde, furan, and pyrrole, were obtained at the nitrogen, oxygen, and carbon K-edges with the Coupled Cluster ansatz (CC) and with the Time-Dependent Density Functional Theory (TDDFT) by treating the inner shell excitations as individual channels, separated from the valence part of the spectrum. The discretized electronic pseudospectrum, obtained with quadratically integrable basis sets ( a.k.a. L2) at the CC or TDDFT level, is used to reconstruct the complex dipole polarizability function, from which the photoabsorption cross section near the K-edge is obtained by a continued fraction based analytic continuation procedure. The CC2 and CCSD results are in good agreement with experimental data, while the TDDFT results yield reliable cross sections. Overall, the results obtained in this work indicate that our method can be used for the treatment of the NEXAFS spectra, with the advantage that the electronic excitations in the K-edges can be easily obtained at low computational cost using TDDFT.