Ab initio calculation of UV-Vis absorption spectra of a single molecule chlorophyll a: Comparison study between RHF/CIS, TDDFT, and semi-empirical methods

TL;DR

This study compares ab initio and semi-empirical computational methods for predicting the UV-Vis absorption spectra of chlorophyll a, highlighting their accuracy, limitations, and insights into the molecule's electronic transitions.

Contribution

It provides a comparative analysis of RHF/CIS, TDDFT, and semi-empirical methods in reconstructing chlorophyll a's spectra, revealing their respective strengths and weaknesses.

Findings

Semi-empirical methods yield better energy scaling factors.

Ab initio methods, especially TDDFT with high basis sets, capture more spectral features.

Scaling is necessary to match experimental spectra.

Abstract

Chlorophyll a is one the most abundant pigment on Earth that responsible for trapping the light energy to perform photosynthesis in green plants. This molecule is a metal-complex that consists of a porphyrin ring with high symmetry that acts as ligands with magnesium as the central ion. Chlorophyll a has been studied for many years from different point of views for both experimental and theoretical interests. In this study, the restricted Hartree-Fock configuration interaction single (RHF/CIS), time-dependent density functional theory (TDDFT) and some semi-empirical methods (CNDO/s and ZINDO) calculations were carried out and compared to reconstruct the UV-Vis absorption spectra of chlorophyll a. In some extend, the calculation results based on a single molecule calculation were succeeded to reconstruct the absorption spectra but required to be scaling to match the experimental one. Different computational methods (ab initio and semi-empirical) exhibit the differences in the energy correction factor and the presence of transition states, however, still conserve the main spectral features. In general, the semi-empirical methods provide a better energy scaling factor, which means closer to the experimental one. However, they lack of fine features or vertical transitions with respect to the experimental spectra. The ab initio calculations result more complete features than the semi-empirical methods, especially the TDDFT with high level of basis sets that provides a good accuracy in transition energies. The contribution of ground states and excited states orbitals in the main vertical transitions is discussed based on orbital structure. This might gives a new perspective to explain the energy transfer phenomena in the absorption processes that related to the function of chlorophyll a as a light-harvesting antenna.