Quantifying the impact of the Tamm–Dancoff approximation on the computed spectra of transition-metal systems

Abstract

The Tamm–Dancoff Approximation (TDA) offers a computationally efficient alternative to full linear-response Time-Dependent Density Functional Theory (TDDFT) for calculating electronic excited states, particularly in large molecular systems. By neglecting the coupling between excitation and de-excitation channels, TDA simplifies the TDDFT response equations into a Hermitian form. This not only reduces computational cost but also eliminates numerical instabilities that can arise in the full non-Hermitian formalism. While TDA has been widely explored for valence excitations, its reliability for transition metal complexes and core-level spectroscopies remains largely untested. In this work, we address this gap by systematically comparing TDA and full TDDFT results for a series of transition metal species, focusing on absorption spectra across the UV–Vis, metal K-edges, and L-edges. Our results show that, for core-level excitations, TDA yields excitation energies and oscillator strengths nearly indistinguishable from those obtained with full TDDFT. This agreement is attributed to the negligible contribution of de-excitation amplitudes at high excitation energies, indicating that the omitted coupling terms play an insignificant role in these spectral regimes.