Interplay between Intra- and Intermolecular Charge Transfer in the Optical Excitations of J-Aggregates

In a first-principles study based on density functional theory and many-body perturbation theory, we address the interplay between intra- and intermolecular interactions in a J-aggregate formed by push-pull organic dyes by investigating its electronic and optical properties. We find that the most intense excitation dominating the spectral onset of the aggregate, i.e., the J-band, exhibits a combination of intramolecular charge transfer, coming from the push-pull character of the constituting dyes, and intermolecular charge transfer, due to the dense molecular packing. We also show the presence of a pure intermolecular charge-transfer excitation within the J-band, which is expected to play a relevant role in the emission properties of the J-aggregate. Our results shed light on the microscopic character of optical excitations of J-aggregates and offer new perspectives to further understand the nature of collective excitations in organic semiconductors.Comment: published under ACS Authorchoice licens

Quantifying the Plasmonic Character of Optical Excitations in a Molecular J-Aggregate

The definition of plasmon at the microscopic scale is far from being understood. Yet, it is very important to recognize plasmonic features in optical excitations, as they can inspire new applications and trigger new discoveries by analogy with the rich phenomenology of metal nanoparticle plasmons. Recently, the concepts of plasmonicity index and the generalized plasmonicity index (GPI) have been devised as computational tools to quantify the plasmonic nature of optical excitations. The question may arise whether any strong absorption band, possibly with some sort of collective character in its microscopic origin, shares the status of plasmon. Here we demonstrate that this is not always the case, by considering a well-known class of systems represented by J-aggregates molecular crystals, characterized by the intense J band of absorption. By means of first-principles simulations, based on a many-body perturbation theory formalism, we investigate the optical properties of a J-aggregate made of push-pull organic dyes. We show that the effect of aggregation is to lower the GPI associated with the J-band with respect to the isolated dye one, which corresponds to a nonplasmonic character of the electronic excitations. In order to rationalize our finding, we then propose a simplified one-dimensional theoretical model of the J-aggregate. A useful microscopic picture of what discriminates a collective molecular crystal excitation from a plasmon is eventually obtained.Comment: Published by ACS under ACS AuthorChoice licens

G0W0G_0W_0 Ionization Potentials of First-Row Transition Metal Aqua Ions

We report computations of the vertical ionization potentials within the $GW$ approximation of the near-complete series of first-row transition metal (V-Cu) aqua ions in their most common oxidation states, i.e. V$^{3+}$, Cr$^{3+}$, Cr$^{2+}$, Mn$^{2+}$, Fe$^{3+}$, Fe$^{2+}$, Co$^{2+}$, Ni$^{2+}$, and Cu$^{2+}$. The $d$-orbital occupancy of these systems spans a broad range from $d^2$ to $d^9$. All the structures were first optimized at the density functional theory level using a large cluster of explicit water molecules that are embedded in a continuum solvation model. Vertical ionization potentials were computed with the one-shot $G_0W_0$ approach on a range of transition metal ion clusters (6, 18, 40, and 60 explicit water molecules) wherein the convergence with respect to the basis set size was evaluated using the systems with 40 water molecules. We assess the results using three different density functional approximations as starting points for the vertical ionization potential calculations, namely $G_0W_0$@PBE, $G_0W_0$@PBE0, and $G_0W_0$@r$^2$SCAN. While the predicted ground-state structures are similar with all three exchange-correlation functionals, the vertical ionization potentials were in closer agreement with the experiment when using the $G_0W_0$@PBE0 and $G_0W_0$@r$^2$SCAN approaches, with the r2SCAN based calculations being significantly less expensive. Computed bond distances and vertical ionization potentials for all structures were compared with available experimental data and are in good agreement

A Density-Based Basis-Set Incompleteness Correction for GW Methods

9 pages, 2 figures (supporting information available)International audienceSimilar to other electron correlation methods, many-body perturbation theory methods based on Green functions, such as the so-called $GW$ approximation, suffer from the usual slow convergence of energetic properties with respect to the size of the one-electron basis set. This displeasing feature is due to lack of explicit electron-electron terms modeling the infamous Kato electron-electron cusp and the correlation Coulomb hole around it. Here, we propose a computationally efficient density-based basis set correction based on short-range correlation density functionals which significantly speeds up the convergence of energetics towards the complete basis set limit. The performance of this density-based correction is illustrated by computing the ionization potentials of the twenty smallest atoms and molecules of the GW100 test set at the perturbative $GW$ (or $G_0W_0$) level using increasingly large basis sets. We also compute the ionization potentials of the five canonical nucleobases (adenine, cytosine, thymine, guanine, and uracil) and show that, here again, a significant improvement is obtained

Assessment of the Ab Initio Bethe-Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls

Bacteriochlorophyll and Chlorophyll molecules are crucial building blocks of the photosynthetic apparatus in bacteria, algae and plants. Embedded in transmembrane protein complexes, they are responsible for the primary processes of photosynthesis: excitation energy and charge transfer. Here, we use ab initio many body perturbation theory within the $GW$ approximation and Bethe-Salpeter equation (BSE) approach to calculate the electronic structure and optical excitations of Bacteriochlorophylls $a$, $b$, $c$, $d$ and $e$ and Chlorophylls $a$ and $b$. We systematically study the effects of structure, basis set size, partial self-consistency in $GW$, and the underlying exchange-correlation approximation, and compare our calculations with results from time-dependent density functional theory, multireference RASPT2 and experimental literature results. We find that optical excitations calculated with $GW$+BSE are in excellent agreement with experimental data, with an average deviation of less than 100\,meV for the first three bright excitations of the entire family of (Bacterio)chlorophylls. Contrary to state-of-the-art TDDFT with an optimally-tuned range-separated hybrid functional, this accuracy is achieved in a parameter-free approach. Moreover, $GW$+BSE predicts the energy differences between the low-energy excitations correctly, and eliminates spurious charge transfer states that TDDFT with (semi)local approximations is known to produce. Our study provides accurate reference results and highlights the potential of the $GW$+BSE approach for the simulation of larger pigment complexes