An improved guess for the variational calculation of charge-transfer excitations in large systems

TL;DR

This paper introduces improved initial guess algorithms and combined minimization schemes to enhance the reliable variational calculation of charge-transfer excited states in large molecular systems, addressing convergence challenges.

Contribution

The authors develop two constrained algorithms for initial guesses and demonstrate their effectiveness in achieving convergence in large systems, advancing variational excited-state DFT methods.

Findings

Reliable convergence achieved for large systems

Effective initial guesses improve variational calculations

Range-separated hybrid functionals provide accurate energy estimates

Abstract

Charge-transfer excited states are highly relevant for applications in molecular electronics. However, the accurate calculation of these states in large systems is challenging since wave function methods are prohibitively expensive, time-dependent density functional theory with typical functionals is not precise, and the complicated topology of the electronic hypersurface makes the variational convergence to the targeted excited states a difficult task. We address the latter aspect by providing suitable initial guesses which we obtain by two separate constrained algorithms. Combined with subsequent squared-gradient minimization schemes, we demonstrate that OO-DFT calculations can reliably converge to the charge-transfer states of interest even for large molecular systems. We test this approach on two chemically very different supramolecular structures and also analyze the performance of two recently proposed methods for the tuning of the range-separation parameter in time-dependent DFT with range-separated hybrid functionals. Our results demonstrate that with the methods presented here, reliable convergence of charge-transfer excited states can be achieved with variational excited-state DFT methods, while time-dependent DFT calculations with an adequate tuning procedure for the range-separation parameter can provide a computationally efficient initial estimate of the corresponding energies.