Linear-scaling time-dependent density-functional theory (TDDFT) beyond the Tamm-Dancoff approximation: obtaining efficiency and accuracy with in situ optimised local orbitals

TL;DR

This paper introduces a linear-scaling TDDFT method that accurately models large molecular systems beyond the Tamm-Dancoff approximation, enabling efficient and precise excitation spectrum calculations including solvent effects.

Contribution

The work develops a full TDDFT approach with in situ optimized local orbitals, achieving linear scaling and improved accuracy over TDA, suitable for large complex systems.

Findings

Accurate absorption spectra of bacteriochlorophyll in solvent

Full TDDFT outperforms TDA in low-energy spectral features

Demonstrated linear-scaling for large molecular systems

Abstract

We present a solution of the full TDDFT eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspace with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate-gradients algorithm that is very memory-efficient. The algorithm is validated on a test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll (BChl) in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of BChl in solution. The largest systems considered in this work are of the same order of magnitude as a variety of pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.