Resolution-of-identity accelerated relativistic two- and four-component electron dynamics approach to chiroptical spectroscopies

Abstract

We present an implementation and application of electron dynamics based on real-time time-dependent density functional theory (RT-TDDFT) and relativistic 2-component X2C and 4-component Dirac–Coulomb (4c) Hamiltonians to the calculation of electron circular dichroism and optical rotatory dispersion spectra. In addition, the resolution-of-identity approximation for the Coulomb term (RI-J) is introduced into RT-TDDFT and formulated entirely in terms of complex quaternion algebra. The proposed methodology was assessed on the dimethylchalcogenirane series, C₄H₈X (X = O, S, Se, Te, Po, Lv), and the spectra obtained by non-relativistic and relativistic methods start to disagree for Se and Te, while dramatic differences are observed for Po and Lv. The X2C approach, even in its simplest one-particle form, reproduces the reference 4c results surprisingly well across the entire series while offering an 8-fold speed-up of the simulations. An overall acceleration of RT-TDDFT by means of X2C and RI-J increases with system size and approaches a factor of almost 25 when compared to the full 4c treatment, without compromising the accuracy of the final spectra. These results suggest that one-particle X2C electron dynamics with RI-J acceleration is an attractive method for the calculation of chiroptical spectra in the valence region.