First-Principle Characterization of Structural, Electronic, and Optical Properties of Tin-Halide Monomers.

The growing interest in tin-halide semiconductors for photovoltaic applications demands an in-depth knowledge of the fundamental properties of their constituents, starting from the smallest monomers entering the initial stages of formation. In this first-principles work based on time-dependent density-functional theory, we investigate the structural, electronic, and optical properties of tin-halide molecules SnXn2-n, with n=1,2,3,4 and X = Cl, Br, I, simulating these compounds in vacuo as well as in an implicit solvent. We find that structural properties are very sensitive to the halogen species while the charge distribution is also affected by stoichiometry. The ionicity of the Sn-X bond is confirmed by the Bader charge analysis albeit charge displacement plots point to more complex metal-halide coordination. Particular focus is posed on the neutral molecules SnX2, for which electronic and optical properties are discussed in detail. Band gaps and absorption onset decrease with increasing size of the halogen species, and despite general common features, each molecule displays peculiar optical signatures. Our results are elaborated in the context of experimental and theoretical literature, including the more widely studied lead-halide analogs, aiming to contribute with microscopic insight to a better understanding of tin-halide perovskites.

Impact of Ligand Substitution and Metal Node Exchange in the Electronic Properties of Scandium Terephthalate Frameworks.

The search for sustainable alternatives to established materials is a sensitive topic in materials science. Due to their unique structural and physical characteristics, the composition of metal-organic frameworks (MOFs) can be tuned by the exchange of metal nodes and the functionalization of organic ligands, giving rise to a large configurational space. Considering the case of scandium terephthalate MOFs and adopting an automatized computational framework based on density-functional theory, we explore the impact of metal substitution with the earth-abundant isoelectronic elements Al and Y, and ligand functionalization of varying electronegativity. We find that structural properties are strongly impacted by metal ion substitution and only moderately by ligand functionalization. In contrast, the energetic stability, the charge density distribution, and the electronic properties, including the size of the band gap, are primarily affected by the termination of the linker molecules. Functional groups such as OH and NH2 lead to particularly stable structures thanks to the formation of hydrogen bonds and affect the electronic structure of the MOFs by introducing midgap states.

Tuning structural and electronic properties of metal-organic framework 5 by metal substitution and linker functionalization.

The chemical flexibility of metal-organic frameworks (MOFs) offers an ideal platform to tune structure and composition for specific applications, from gas sensing to catalysis and from photoelectric conversion to energy storage. This variability gives rise to a large configurational space that can be efficiently explored using high-throughput computational methods. In this work, we investigate from first principles the structural and electronic properties of MOF-5 variants obtained by replacing Zn with Be, Mg, Cd, Ca, Sr, and Ba and by functionalizing the originally H-passivated linkers with CH3, NO2, Cl, Br, NH2, OH, and COOH groups. To build and analyze the resulting 56 structures, we employ density-functional theory calculations embedded in an in-house developed library for automatized calculations. Our findings reveal that structural properties are mainly defined by metal atoms and large functional groups, which distort the lattice and modify coordination. The formation energy is largely influenced by functionalization and enhanced by COOH and OH groups, which promote the formation of hydrogen bonds. The charge distribution within the linker is especially influenced by functional groups with electron-withdrawing properties, while the metal nodes play a minor role. Likewise, the bandgap size is crucially determined by ligand functionalization. The smallest gaps are found with NH2 and OH groups, which introduce localized orbitals at the top of the valence band. This characteristic makes these functionalizations particularly promising for the design of MOF-5 variants with enhanced gas uptake and sensing properties.

Electronic Structure and Core Spectroscopy of Scandium Fluoride Polymorphs.

Microscopic knowledge of the structural, energetic, and electronic properties of scandium fluoride is still incomplete despite the relevance of this material as an intermediate for the manufacturing of Al-Sc alloys. In a work based on first-principles calculations and X-ray spectroscopy, we assess the stability and electronic structure of six computationally predicted ScF3 polymorphs, two of which correspond to experimentally resolved single-crystal phases. In the theoretical analysis based on density functional theory (DFT), we identify similarities among the polymorphs based on their formation energies, charge-density distribution, and electronic properties (band gaps and density of states). We find striking analogies between the results obtained for the low- and high-temperature phases of the material, indirectly confirming that the transition occurring between them mainly consists of a rigid rotation of the lattice. With this knowledge, we examine the X-ray absorption spectra from the Sc and F K-edge contrasting first-principles results obtained from the solution of the Bethe-Salpeter equation on top of all-electron DFT with high-energy-resolution fluorescence detection measurements. Analysis of the computational results sheds light on the electronic origin of the absorption maxima and provides information on the prominent excitonic effects that characterize all spectra. A comparison with measurements confirms that the sample is mainly composed of the high- and low-temperature polymorphs of ScF3. However, some fine details in the experimental results suggest that the probed powder sample may contain defects and/or residual traces of metastable polymorphs.

Electronic Structure and Optical Properties of Tin Iodide Solution Complexes.

The emerging interest in tin halide perovskites demands a robust understanding of the fundamental properties of these materials starting from the earliest steps of their synthesis. In a first-principles work based on time dependent density functional theory, we investigate the structural, energetic, electronic, and optical properties of 14 tin iodide solution complexes formed by the SnI2 unit tetracoordinated with molecules of common solvents, which we classify according to their Gutmann's donor number. We find that all considered complexes are energetically stable and their formation energy expectedly increases with the donating ability of the solvent. The energies of the frontier states are affected by the choice of solvent, with their absolute values decreasing with the donor number. The occupied orbitals are predominantly localized on the tin iodide unit, while the unoccupied ones are distributed also on the solvent molecules. Owing to this partial wave function overlap, the first optical excitation is generally weak, although the spectral weight is red-shifted by the solvent molecules being coordinated to SnI2 in comparison to the reference obtained for this molecule alone. Comparisons with results obtained on the same level of theory on Pb-based counterparts corroborate our analysis. The outcomes of this study provide quantum-mechanical insight into the fundamental properties of tin iodide solution complexes. This knowledge is valuable in the research on lead-free halide perovskites and their precursors.

Pulse-Induced Dynamics of a Charge-Transfer Complex from First Principles.

The ultrafast dynamics of charge carriers in organic donor-acceptor interfaces are of primary importance to understanding the fundamental properties of these systems. In this work, we focus on a charge-transfer complex formed by quaterthiophene p-doped by tetrafluoro-tetracyanoquinodimethane and investigate electron dynamics and vibronic interactions also at finite temperatures by applying a femtosecond pulse in resonance with the two lowest energy excitations of the system with perpendicular and parallel polarization with respect to the interface. The adopted ab initio formalism based on real-time time-dependent density-functional theory coupled to Ehrenfest dynamics enables monitoring the dynamical charge transfer across the interface and assessing the role played by the nuclear motion. Our results show that the strong intermolecular interactions binding the complex already in the ground state influence the dynamics, too. The analysis of the nuclear motion involved in these processes reveals the participation of different vibrational modes depending on the electronic states stimulated by the resonant pulse. Coupled donor-acceptor modes mostly influence the excited state polarized across the interface, while intramolecular vibrations in the donor molecule dominate the excitation in the orthogonal direction. The results obtained at finite temperatures are overall consistent with this picture, although thermal disorder contributes to slightly decreasing interfacial charge transfer.

Donors, acceptors, and a bit of aromatics: electronic interactions of molecular adsorbates on hBN and MoS2 monolayers.

The design of low-dimensional organic-inorganic interfaces for the next generation of opto-electronic applications requires in-depth understanding of the microscopic mechanisms ruling electronic interactions in these systems. In this work, we present a first-principles study based on density-functional theory inspecting the structural, energetic, and electronic properties of five molecular donors and acceptors adsorbed on freestanding hexagonal boron nitride (hBN) and molybdenum disulfide (MoS2) monolayers. All considered interfaces are stable, due to the crucial contribution of dispersion interactions, which are maximized by the overall flat arrangement of the physisorbed molecules on both substrates. The level alignment of the hybrid systems depends on the characteristics of the constituents. On hBN, both type-I and type-II interfaces may form, depending on the relative energies of the frontier orbitals with respect to the vacuum level. On the other hand, all MoS2-based hybrid systems exhibit a type-II level alignment, with the molecular frontier orbitals positioned across the energy gap of the semiconductor. The electronic structure of the hybrid materials is further determined by the formation of interfacial dipole moments and by the wave-function hybridization between the organic and inorganic constituents. These results provide important indications for the design of novel low-dimensional hybrid materials with suitable characteristics for opto-electronics.

Understanding the evolution of the Raman spectra of molecularly p-doped poly(3-hexylthiophene-2,5-diyl): signatures of polarons and bipolarons.

Molecular doping is a key process to increase the density of charge carriers in organic semiconductors. Doping-induced charges in polymer semiconductors result in the formation of polarons and/or bipolarons due to the strong electron-vibron coupling in conjugated organic materials. Identifying the nature of charge carriers in doped polymers is essential to optimize the doping process for applications. In this work, we use Raman spectroscopy to investigate the formation of charge carriers in molecularly doped poly(3-hexylthiophene-2,5-diyl) (P3HT) for increasing dopant concentration, with the organic salt dimesityl borinium tetrakis(penta-fluorophenyl)borate (Mes2B+ [B(C6F5)4]-) and the Lewis acid tris(pentafluorophenyl)borane [B(C6F5)3]. While the Raman signatures of neutral P3HT and singly charged P3HT segments (polarons) are known, the Raman spectra of doubly charged P3HT segments (bipolarons) are not yet sufficiently understood. Combining Raman spectroscopy measurements on doped P3HT thin films with first-principles calculations on oligomer models, we explain the evolution of the Raman spectra from neutral P3HT to increasingly doped P3HT featuring polarons and eventually bipolarons at high doping levels. We identify and explain the origin of the spectral features related to bipolarons by tracing the Raman signature of the symmetric collective vibrations along the polymer backbone, which - compared to neutral P3HT - redshifts for polarons and blueshifts for bipolarons. This is explained by a planarization of the singly charged P3HT segments with polarons and rather high order in thin films, while the doubly charged segments with bipolarons are located in comparably disordered regions of the P3HT film due to the high dopant concentration. Furthermore, we identify additional Raman peaks associated with vibrations in the quinoid doubly charged segments of the polymer. Our results offer the opportunity for readily identifying the nature of charge carriers in molecularly doped P3HT while taking advantage of the simplicity, versatility, and non-destructive nature of Raman spectroscopy.

Exploring cesium-tellurium phase space via high-throughput calculations beyond semi-local density-functional theory.

Boosted by the relentless increase in available computational resources, high-throughput calculations based on first-principles methods have become a powerful tool to screen a huge range of materials. The backbone of these studies is well-structured and reproducible workflows efficiently returning the desired properties given chemical compositions and atomic arrangements as sole input. Herein, we present a new workflow designed to compute the stability and the electronic properties of crystalline materials from density-functional theory using the strongly constrained and appropriately normed approximation (SCAN) for the exchange-correlation potential. We show the performance of the developed tool exploring the binary Cs-Te phase space that hosts cesium telluride, a semiconducting material widely used as a photocathode in particle accelerators. Starting from a pool of structures retrieved from open computational material databases, we analyze formation energies as a function of the relative Cs content and for a few selected crystals, we investigate the band structures and density of states unraveling interconnections among the structure, stoichiometry, stability, and electronic properties. Our study contributes to the ongoing research on alkali-based photocathodes and demonstrates that high-throughput calculations based on state-of-the-art first-principles methods can complement experiments in the search for optimal materials for next-generation electron sources.

Optimized Synthesis of Solution-Processable Crystalline Poly(Triazine Imide) with Minimized Defects for OLED Application.

Poly(triazine imide) (PTI) is a highly crystalline semiconductor, and though no techniques exist that enable synthesis of macroscopic monolayers of PTI, it is possible to study it in thin layer device applications that are compatible with its polycrystalline, nanoscale morphology. We find that the by-product of conventional PTI synthesis is a C-C carbon-rich phase that is detrimental for charge transport and photoluminescence. An optimized synthetic protocol yields a PTI material with an increased quantum yield, enabled photocurrent and electroluminescence. We report that protonation of the PTI structure happens preferentially at the pyridinic N atoms of the triazine rings, is accompanied by exfoliation of PTI layers, and contributes to increases in quantum yield and exciton lifetimes. This study describes structure-property relationships in PTI that link the nature of defects, their formation, and how to avoid them with the optical and electronic performance of PTI. On the basis of our findings, we create an OLED prototype with PTI as the active, metal-free material.

Exploring organic semiconductors in solution: the effects of solvation, alkylization, and doping.

The first-principles simulation of the electronic structure of organic semiconductors in solution poses a number of challenges that are not trivial to address simultaneously. In this work, we investigate the effects and the mutual interplay of solvation, alkylization, and doping on the structural, electronic, and optical properties of sexithiophene, a representative organic semiconductor molecule. To this end, we employ (time-dependent) density functional theory in conjunction with the polarizable-continuum model. We find that the torsion between adjacent monomer units plays a key role, as it strongly influences the electronic structure of the molecule, including energy gap, ionization potential, and band widths. Alkylization promotes delocalization of the molecular orbitals up to the first methyl unit, regardless of the chain length, leading to an overall shift of the energy levels. The alterations in the electronic structure are reflected in the optical absorption, which is additionally affected by dynamical solute-solvent interactions. Taking all these effects into account, solvents decrease the optical gap by an amount that depends on its polarity, and concomitantly increase the oscillator strength of the first excitation. The interaction with a dopant molecule promotes planarization. In such scenario, solvation and alkylization enhance charge transfer both in the ground state and in the excited state.

First-principles analysis of the optical properties of lead halide perovskite solution precursors.

Lead halide perovskites (LHPs) are promising materials for opto-electronics and photovoltaics, thanks to favorable characteristics and low manufacturing costs enabled by solution processing. In light of this, it is crucial to assess the impact of solvent-solute interactions on the electronic and optical properties of LHPs and of their solution precursors. In a first-principles work based on time-dependent density-functional theory coupled with the polarizable continuum model, we investigate the electronic and optical properties of a set of charge-neutral compounds with chemical formula, PbX2(Sol)4, where X = Cl, Br, and I, and Sol are the six common solvents. We find that single-particle energies and optical gaps depend on the halogen species as well as on the solvent molecules, which also affect the energy and the spatial distribution of the molecular orbitals, thereby impacting on the excitations. We clarify that dark states at the absorption onset are promoted by electron-withdrawing solvents, and we show the correlation between oscillator strength and HOMO → LUMO contribution to the excitations. Our results provide microscopic insight into the electronic and optical properties of LHP solution precursors, complementing ongoing experimental research on these systems and on their evolution to photovoltaic thin films.

Nonlinear light absorption in many-electron systems excited by an instantaneous electric field: a non-perturbative approach.

Applications of low-cost non-perturbative approaches in real time, such as time-dependent density functional theory, for the study of nonlinear optical properties of large and complex systems are gaining increasing popularity. However, their assessment still requires the analysis and understanding of elementary dynamical processes in simple model systems. Motivated by the aim of simulating optical nonlinearities in molecules, here exemplified by the case of the quaterthiophene oligomer, we investigate light absorption in many-electron interacting systems beyond the linear regime by using a single broadband impulse of an electric field; i.e. an electrical impulse in the instantaneous limit. We determine non-pertubatively the absorption cross section from the Fourier transform of the time-dependent induced dipole moment, which can be obtained from the time evolution of the wavefunction. We discuss the dependence of the resulting cross section on the magnitude of the impulse and we highlight the advantages of this method in comparison with perturbation theory by working on a one-dimensional model system for which numerically exact solutions are accessible. Thus, we demonstrate that the considered non-pertubative approach provides us with an effective tool for investigating fluence-dependent nonlinear optical excitations.

Laser-Induced Electronic and Vibronic Dynamics in the Pyrene Molecule and Its Cation.

Among polycyclic aromatic hydrocarbons, pyrene is widely used as an optical probe thanks to its peculiar ultraviolet absorption and infrared emission features. Interestingly, this molecule is also an abundant component of the interstellar medium, where it is detected via its unique spectral fingerprints. In this work, we present a comprehensive first-principles study on the electronic and vibrational response of pyrene and its cation to ultrafast, coherent pulses in resonance with their optically active excitations in the ultraviolet region. The analysis of molecular symmetries, electronic structure, and linear optical spectra is used to interpret transient absorption spectra and kinetic energy spectral densities computed for the systems excited by ultrashort laser fields. By disentangling the effects of the electronic and vibrational dynamics via ad hoc simulations with stationary and moving ions, and, in specific cases, with the aid of auxiliary model systems, we rationalize that the nuclear motion is mainly harmonic in the neutral species, while strong anharmonic oscillations emerge in the cation, driven by electronic coherence. Our results provide additional insights into the ultrafast vibronic dynamics of pyrene and related compounds and set the stage for future investigations on more complex carbon-conjugated molecules.

LayerPCM: An implicit scheme for dielectric screening from layered substrates.

We present LayerPCM, an extension of the polarizable-continuum model coupled to real-time time-dependent density-functional theory, for an efficient and accurate description of the electrostatic interactions between molecules and multilayered dielectric substrates on which they are physisorbed. The former are modeled quantum-mechanically, while the latter are treated as polarizable continua characterized by their dielectric constants. The proposed approach is purposely designed to simulate complex hybrid heterostructures with nano-engineered substrates including a stack of anisotropic layers. LayerPCM is suitable for describing the polarization-induced renormalization of frontier energy levels of the adsorbates in the static regime. Moreover, it can be reliably applied to simulating laser-induced ultrafast dynamics of molecules through the inclusion of electric fields generated by Fresnel-reflection at the substrate. Depending on the complexity of the underlying layer structure, such reflected fields can assume non-trivial shapes and profoundly affect the dynamics of the photo-excited charge carriers in the molecule. In particular, the interaction with the substrate can give rise to strong delayed fields, which lead to interference effects resembling those of multi-pulse-based spectroscopy. The robustness of the implementation and the above-mentioned features are demonstrated with a number of examples, ranging from intuitive models to realistic systems.

Ab initio modelling of local interfaces in doped organic semiconductors.

Doping in organic semiconductors remains a debated issue from both an experimental and ab initio perspective. Due to the complexity of these systems, which exhibit a low degree of crystallinity and high level of disorder, modelling doped organic semiconductors from first-principles calculations is not a trivial task, as their electronic and optical properties are sensitive to the choice of initial geometries. A crucial aspect to take into account, in view of rationalizing the electronic structure of these materials through ab initio calculations, is the role of local donor/acceptor interfaces. We address this problem in the framework of state-of-the-art density-functional theory and many-body perturbation theory, investigating the structural, electronic, and optical properties of quaterthiophene and sexithiophene oligomers doped by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ). We consider different model structures ranging from isolated dimers and trimers, to periodic stacks. Our results demonstrate that the choice of the initial geometry critically impacts the resulting electronic structure and the degree of charge transfer in the materials, depending on the amount and on the nature of the local interfaces between donor and acceptor species. The optical spectra appear less sensitive to these parameters at least from a first glance, although a quantitative analysis of the excitations reveals that their Frenkel or charge-transfer character is affected by the characteristics of the donor/acceptor interfaces as well as by the donor length. Our findings represent an important step forward towards an insightful first-principles description of the microscopic properties of doped organic semiconductors complementary to experiments.

Understanding real-time time-dependent density-functional theory simulations of ultrafast laser-induced dynamics in organic molecules.

Real-time time-dependent density functional theory, in conjunction with the Ehrenfest molecular dynamics scheme, is becoming a popular methodology to investigate ultrafast phenomena on the nanoscale. Thanks to recent developments, it is also possible to explicitly include in the simulations a time-dependent laser pulse, thereby accessing the transient excitation regime. However, the complexity entailed in these calculations calls for in-depth analysis of the accessible and yet approximate (either "dressed" or "bare") quantities in order to evaluate their ability to provide us with a realistic picture of the simulated processes. In this work, we analyze the ultrafast dynamics of three small molecules (ethylene, benzene, and thiophene) excited by a resonant laser pulse in the framework of the adiabatic local-density approximation. The electronic response to the laser perturbation in terms of induced dipole moment and excited-state population is compared to the results given by an exactly solvable two-level model. In this way, we can interpret the charge-carrier dynamics in terms of simple estimators, such as the number of excited electrons. From the computed transient absorption spectra, we unravel the appearance of nonlinear effects such as excited-state absorption and vibronic coupling. In this way, we observe that the laser excitation affects the vibrational spectrum by enhancing the anharmonicities therein, while the coherent vibrational motion contributes to stabilizing the electronic excitation already within a few tens of femtoseconds.

Polarized absorbance and Davydov splitting in bulk and thin-film pentacene polymorphs.

Pentacene is one of the most studied organic materials and in particular its optical properties have been the subject of intense research during the last two decades. In spite of such a widespread interest and of the extensive knowledge achieved so far, a number of issues are still debated. One of the most relevant questions concerns the role of polymorphism and how it affects the lowest-energy exciton, which appears in the visible region and is subject to a sizable Davydov splitting. We address this problem in a combined theoretical and experimental work, where the optical absorption properties of three pentacene polymorphs are investigated within the whole energy range of visible light. Optical spectra computed from first principles in the framework of many-body perturbation theory are directly compared with the polarization-resolved absorbance, measured for three different pentacene phases (the two bulk polymorphs and the thin-film phase). In this way, we unambiguously identify the two Davydov components of the first exciton and the optical fingerprints of each considered phase. With very good agreement between theory and experiment, we show that all polymorphs exhibit common features at the absorption onset, while phase-dependent characteristics appear only above 2 eV. We discuss the character of the lowest-lying singlet and triplet excitons, including dark ones, highlighting the contributions from the electronic bands and the role of the electron-hole interaction and of the local-field effects.

Molecular structure of the substrate-induced thin-film phase of tetracene.

We present a combined experimental and theoretical study to solve the unit-cell and molecular arrangement of the tetracene thin film (TF) phase. TF phases, also known as substrate induced phases (SIPs), are polymorphs that exist at interfaces and decisively impact the functionality of organic thin films, e.g., in a transistor channel, but also change the optical spectra due to the different molecular packing. As SIPs only exist in textured ultrathin films, their structure determination remains challenging compared to bulk materials. Here, we use grazing incidence X-ray diffraction and atomistic simulations to extract the TF unit-cell parameters of tetracene together with the atomic positions within the unit-cell.