Valence and Rydberg excited state bond dissociation curves of CO2 from orbital-optimized density functional calculations

TL;DR

This study demonstrates that orbital-optimized density functional calculations effectively model excited states and bond dissociation in CO2 with low computational cost, showing good agreement with high-level methods.

Contribution

It introduces an orbital-optimized DFT approach for excited states that is computationally efficient and yields accurate results compared to multireference methods.

Findings

PBE with complex orbitals yields excitation energies within 0.3 eV of reference values.

Orbital-optimized calculations outperform linear-response TDDFT for diffuse Rydberg states.

Calculated dissociation curves agree well with high-level multireference and coupled-cluster methods.

Abstract

Calculations of the lowest valence {\pi}* as well as the 3s and higher energy 3p{\sigma} Rydberg excited states of the CO2 molecule are carried out using density functionals with variational optimization of the orbitals, an approach involving relatively little computational effort. Five functionals with varying degree of exchange are used in combination with real or complex-valued orbitals that are optimized by finding saddle points on the electronic energy surface corresponding to the excited states. When the PBE functional is used in combination with complex orbitals, the calculated excitation energy is found to be within 0.3 eV of multireference configuration interaction reference values, and the results are further improved with hybrid functionals. In contrast, linear-response time-dependent density functional theory calculations give errors up to 1.9 eV for the most diffuse 3p{\sigma} excitation and exhibit stronger dependence on both the excitation character and the functional used. Calculated C-O dissociation curves using the PBE functional and the orbital-optimized approach compare remarkably well with the reported multireference configuration interaction and equation-of-motion coupled-cluster singles and doubles calculations. Thanks to the low computational cost, these results demonstrate that orbital-optimized density functional calculations can be a promising route for modelling photorelaxation in condensed-phase CO2, for example in the context of interstellar cosmic-ray radiation driven process involving high-energy Rydberg states.