Revealing the impact of organic spacers and cavity cations on quasi-2D perovskites via computational simulations

Two-dimensional hybrid lead iodide perovskites based on methylammonium (MA) cation and butylammonium (BA) organic spacer—such as BA2MAn−1PbnI3n+1—are one of the most explored 2D hybrid perovskites in recent years. Correlating the atomistic profile of these systems with their optoelectronic properties is a challenge for theoretical approaches. Here, we employed first-principles calculations via density functional theory to show how the cation partially canceled dipole moments through the NH3+ terminal impact the structural/electronic properties of the PbnI3n+1 sublattices. Even though it is known that at high temperatures, the organic cation assumes a spherical-like configuration due to the rotation of the cations inside the cage, our results discuss the correct relative orientation according to the dipole moments for ab initio simulations at 0 K, correlating well structural and electronic properties with experiments. Based on the combination of relativistic quasiparticle correction and spin-orbit coupling, we found that the MA horizontal-like configuration concerning the inorganic sublattice surface leads to the best relationship between calculated and experimental gap energy throughout n = 1, 2, 3, 4, and 5 number of layers. Conversely, the dipole moments cancellation (as in BA-MA aligned-like configuration) promotes the closing of the gap energies through an electron depletion mechanism. We found that the anisotropy → isotropy optical absorption conversion (as a bulk convergence) is achieved only for the MA horizontal-like configuration, which suggests that this configuration contribution is the majority in a scenario under temperature effects

Unveiling oxygen vacancy impact on lizardite thermo and mechanical properties

Here, we performed a systematic DFT study assisted by the workflow framework SimStack for the mechanical and thermodynamic properties of the clay mineral lizardite in pristine and six different types of O vacancies configurations. In most cases, the defect caused a structural phase transition in the lizardite from the trigonal (pristine) to the triclinic phase. The results show that oxygen vacancies in lizardite significantly reduce the lattice thermal conductivity, accompanied by an elastic moduli reduction and an anisotropy index increase. Through the P–V relation, an increase in compressibility was evidenced for vacancy configurations. Except for the vacancy with the same crystalline structure as pristine lizardite, the sound velocities of the other vacancy configurations produce a decrease in these velocities, and it is essential to highlight high values for the Grüneisen parameter. We emphasize the great relevance of the punctual-defects introduction, such as O vacancies, in lizardite, since this microstructural design is responsible for the decrease of the lattice thermal conductivity in comparison with the pristine system by decreasing the heat transfer ability, turning lizardite into a promising candidate for thermoelectric materials

Ab initio Study of the Ligands and Temperature Effects on the Stability and Meta-stability of Metallic Nanoclusters

Nanoclusters de metais de transição (TM) com dimensões de &#126;1,0 nm têm atraído grande interesse em diversas aplicações tecnológicas, como microeletrônica, óptica, dispositivos magnéticos e principalmente como nanocatalisadores. Nesse contexto, a morfologia desses sistemas é um fator fundamental para otimzação de performace nessas aplicações, tendo em vista a relação direta entre as propriedades físico-químicas e a estrutura atômica do nanocluster determinada pelas condições do ambiente (temperatura e moléculas adsorvidas). No entanto, diante das limitações relativas à precisão das técnicas de caracterização experimental disponíveis atualmente, sobretudo em dimensões nanométricas, o uso de cálculos computacionais através de métodos de primeiros princípios (ab initio) e baseados na teoria do funcional da densidade se torna indispensável. Neste trabalho, foram investigados os efeitos de ligantes e temperaturas nas propriedades estruturais, eletrônicas, estabilidade e meta-estabilidade de nanoclusters de TM. (i) Os efeitos de ligantes de (PH3)n e (SH2)n (saturação gradativa em n = 1, 6, 12 e 18) adsorvidos em nanoclusters unários de Pt55 e Au55 com estruturas icosaédricas (ICO), cuboctaédricas (CUB) e desordenadas de core reduzido (DRC) foram estudados a 0K. Em fase gasosa, as estruturas DRC com 7 e 9 átomos na região do core são 5,34 eV (Pt55) e 2,20 eV (Au55) mais estáveis que modelo ICO com simetria Ih com 13 átomos no core. Os resultados mostraram que existe uma forte compressão do core catiônico pela superfície aniônica induzida por interações de Coulomb (core+-superfície-), levando ao colapso e redução de estresse das estruturas simétricas a partir da redução do número de átomos na região do core. No entanto, a estabilidade da estrutura ICO aumenta com o aumento do número de moléculas adsorvidas, de modo que DRC e ICO se tornam energeticamente degeneradas em < 0,5 eV. Além disso, a adição de ligantes na superfície aniônica reduz a transferência de cargas entre as regiões de core+-superfície-, contribuindo para a redução das interações de Coulomb e, consequentemente, aliviando o estresse interno da estrutura ICO. Resultados similares foram obtidos utilizando ligantes de trifenilfosfina (PPh3), nos quais as longas cadeias carbônicas adicionam interações laterais entre os ligantes. (ii) Nanoclusters de binários de PtnCo(55 - n) a 0K mostraram alta estabilidade em todo intervalo de composições, indicando uma correlação direta entre estabilidade e distribuição homogênea de átomos de Pt e Co formando a nanoliga com estrutura ICO. No entanto, sob uma atmosfera saturada de ligantes de CO adsorvidos, a estabilidade da nanoliga diminui (aumenta) para composições com grandes quantidades de Pt (Co). As análises mostraram que sob os efeitos da adsorção as composições permanecem com configuração ICO, exceto para Pt42Co13 (estrutura core@shell do tipo Co@Pt em fase gasosa), onde as moléculas de CO deslocam os átomos de Co para a superfície, e, então, induzindo um processo de amorfização na formação de uma estrutura formada com átomos de Pt ocupando o core. Para investigar os efeitos de temperatura na estabilidade e meta-estabilidade de nanoclusters e clusters de Au utilizando dinâmica molecular de Born-Oppenheimer, foram utilizados nanoclusters de tamanho médio de Au25, Au38 e Au40 em fase gasosa e clusters de Au13 sob diferentes atmosferas saturadas de CO. (iii) Observou-se que em temperaturas de 300, 400, 500 e 600 K os nanoclusters exibem estruturas dinâmicas para as regiões de core-superfície, com core tetraédrico (4 átomos) ou T-bipiramidal (5 átomos) catiônicos fracamente ligados à superfície aniônica flexível. Uma abordagem estatística através de um algoritmo de redução de dimensionalidades para representação no espaço euclideano bidimensional, chamado de sketch-map, foi proposta como uma nova linguagem para analisar a superfície de energia livre (FES) dos sistemas calculada na aproximação de multistate Bennet acceptance-ratio. A FES foi utilizada como uma análise qualitativa das configurações estáveis e meta-estáveis sob os efeitos de temperaturas, indicando as regiões preferenciais do espaço configuracional de cada nanocluster investigado. (iv) Incluindo os efeitos de ligantes e temperaturas em clusters de Au13, foi observado que em altas temperaturas os clusters de Au13 em fase gasosa tendem a configurações mais abertas com menor comprimento de ligação com relação às estruturas tridimensionais. Por outro lado, a saturação do ambiente com ligantes de CO restringem a mobilidade dos átomos nos clusters de Au13, favorecendo a amostragem de estruturas tridimensionais mesmo em temperaturas relativamente altas. A análise de população de cargas mostrou uma alta concentração de elétrons nos átomos de O, de modo que o forte catiônico dos clusters de Au13 leva ao aumento da coordenação atômica, contribuindo para a estabilização das estruturas mais tridimensionais.Transition metal nanoclusters (TM) with dimensions of &#126;1,0 nm have attracted great interest in various technological applications such as microelectronics, optics, magnetic devices and mainly as nanocatalysts. In this way, the morphology of these systems is a fundamental factor for optimization of performance in these applications, considering the direct relationship between the physicochemical properties and the atomic structure of the nanocluster determined by the ambient conditions (temperature and adsorbed molecules). In this sense, in view of the limitations on the precision of the experimental characterization techniques currently available, especially in nanometric dimensions, the use of computational calculations using first principles methods (ab initio) and based on the density functional theory is indispensable. Thus, in this work, the effects of binders and temperatures on the structural, electronic properties, stability and metastability of TM nanoclusters were investigated. (i) In this way, the (PH3)n and (SH2)n ligands effects with gradual saturation at n = 1, 6, 12 and 18 adsorbed onto nanoclusters Pt55 and Au55 with icosahedral (ICO), cuboctahedron (CUB), and distorted reduced core (DRC) structures were studied at 0K. In the gas phase, the DRC structures with 7 and 9 atoms in the core region are 5,34 eV (Pt55) and 2,20 eV (Au55) more stable than ICO model with symmetry Ih with 13 atoms in core. The results showed that there is a strong compression of the cationic core by the anionic surface induced by interactions of Coulomb (core+-surface-), leading to collapse and stress reduction of the symmetrical structures from the reduction of the number of atoms in the core region. However, the stability of the ICO structure increases with increasing Number of molecules adsorbed, so that DRC and ICO become approximately degenerated in energy in < 0,5 eV. In addition, ligands on the anionic surface reduces the transfer of charges between core+- surface-, contributing to the reduction of interactions of Coulomb and, consequently, alleviating the internal stress of the ICO. Similar result were obtained using triphenylphosphine (PPh3) as large ligands, in which the long carbon chains add side interactions between the ligands. (ii) PtnCo(55 - n) binares nanoclusters at 0K showed a high stability across the range of compositions, indicating a direct correlation between stability and homogeneous distribution of Pt and Co atoms forming the nanoalloys with ICO structure. However, under a saturated atmosphere of adsorbed CO ligands, the stability of the nanoaaloys decreases (increases) to compositions with large amounts of Pt (Co). Analyzes have shown that under the effects of adsorption the compositions remain with ICO configuration, except for Pt42Co13 (Co@Pt as core@shell in gas-phase), where Co molecules displace the Co atoms to the surface, and then inducing an amorphization process for a structure formed with Pt atoms occupying the core. To investigate the temperature effects on the stability and metastability of Au nanoclusters and clusters by using Born-Oppenheimer molecular dynamics, medium size nanoclusters of Au25, Au38, and Au40 were used in gas-phase and clusters of Au13 under different saturated atmospheres of CO. (iii) It has been observed that at temperatures of 300, 400, 500, and 600 K, the nanoclusters exhibit dynamic structures for the core-surface regions with cationic tetrahedral (4 atoms) or T-bipyramidal (5 atoms) cores weakly bound to the flexible anionic surface. A statistical approach using a dimensionality reduction algorithm for two-dimensional Euclidean space representation, called sketch-map, was proposed as a new language to analyze the free energy surface (FES) of the systems calculated on the approximation of multistate Bennet acceptance-ratio. The FES was used as a qualitative analysis of the stable and metastable configurations under the effect of temperature, indicating the preferred regions of the configurational space of each nanocluster investigated. (iv) By including the effects of ligands and temperatures on Au13 clusters, it was observed that at high temperatures the Au13 clusters in gas-phase tend to have more open configurations with less bond length relative to three-dimensional structures. On the other hand, the saturation of the environment with CO ligands restricts the mobility of the atoms in Au13 clusters, favoring the sampling of three-dimensional structures even at temperatures relatively high. The charge population analysis showed a high concentration of electrons in the O atoms, so that the strong cationic character of the Au13 clusters leads to increased atomic coordination, contributing to the stabilization of the more three-dimensional

Theoretical Investigation of the Adsorption Properties of CO, NO, and OH on Monometallic and Bimetallic 13-Atom Clusters: The Example of Cu₁₃, Pt₇Cu₆, and Pt₁₃

We report a density functional theory investigation of the adsorption properties of CO, NO, and OH on the Cu₁₃, Pt₇Cu₆, and Pt₁₃ clusters in the cationic, neutral, and anionic states with the aim to improve our atomistic understanding of the adsorption properties on bimetallic clusters compared with monometallic clusters. The adsorption energy of CO and NO are substantially stronger on Pt₁₃ than on Cu₁₃, and hence, CO and NO bind preferentially on Pt sites on Pt₇Cu₆. Thus, it can contribute to drive the migration of the Pt atoms from the core to the surface region in large PtCu nanoalloys. The CO and NO adsorption energies on the bimetallic cluster are enhanced by a few percent compared with the energies of the monometallic clusters, which shows that the Pt–Cu interaction can contribute to an increase in the adsorption energy. In contrast with CO and NO trends, the OH adsorption energies on Cu₁₃, Pt₇Cu₆, and Pt₁₃ deviates only up to 0.31 eV, and hence, there is no clear preference for Cu or Pt sites on Pt₇Cu₆ or an enhancement of the adsorption energy on the bimetallic systems. We found a reduction of the CO and NO vibrational frequencies upon adsorption, which indicates a weakening of the CO and NO binding energies, and it is supported by a slight increase in the bond lengths. However, the OH vibrational frequency increases upon adsorption, which indicates an enhancement of the OH binding energy, which is supported by a slight decrease in the bond length by about 0.01 Å. It can be explained by the large charge transfer from the clusters to the O atom, which enhances the electrostatic interaction in the O–H bonding

Comparison of the Performance of van der Waals Dispersion Functionals in the Description of Water and Ethanol on Transition Metal Surfaces

Pairwise van der Waals (vdW) corrections have been routinely added to density functional theory (DFT) adsorption studies of inorganic or organic molecules on solid surfaces, however, comparative studies of the available pairwise corrections, e.g., D2, D3, D3­(BJ), TS, and TS+SCS, are quite scarce. We report DFT calculations within the Perdew–Burke–Ernzerhof (PBE) functional to assess the performance of the mentioned pairwise vdW corrections for well-defined transition-metal (TM) systems, namely, the Cu, Pt, and Au bulks in the face-centered cubic structure, close-packed TM substrates (Cu(111), Pt(111), Au(111), Cu₉/Pt₉/Cu­(111), Pt₉/Cu₉/Cu­(111), Au₉/Pt₉/Au­(111), Pt₉/Au₉/Au­(111)), and the adsorption of water and ethanol on the selected substrates, which include strained Pt-monolayers, i.e., a good challenge for pairwise vdW corrections. In general, accounting for vdW interactions leads to smaller lattice constants, which is expected due to the attractive nature of the vdW corrections, and the D3, D3­(BJ), and TS+SCS improves the DFT-PBE results, in contrast with D2 and TS. Compared with PBE results, the vdW corrections enhance the contraction of the topmost surface layers, which contributes to change the electronic structure, in particular, the d-band center shifts away from the Fermi energy (up to 0.3 eV) in most cases, while the work function changes by about 0.2 eV in the worst cases. As expected, the attractive nature of the vdW corrections helps to enhance adsorption energies by 3–4 times compared with DFT-PBE. However, the adsorption energy trends versus the d-band center are preserved for all vdW corrections, except for the DFT-D2 framework, which deviates substantially from the studied vdW corrections. Therefore, based on our results and analyses, we can conclude that the D3, D3­(BJ), and TS+SCS corrections yield the best description for the selected systems

<i>Ab Initio</i> Investigation of the Role of CO Adsorption on the Physical Properties of 55-Atom PtCo Nanoalloys

The knowledge of the physical and chemical properties of PtCo nanoparticles as a function of the Pt/Co composition and atomic distribution is crucial for several potential applications, which includes catalysis, anticorrosion, data storage, etc. However, our current atom-level understanding is far from satisfactory, in particular due to the challenges to take into account chemical environment effects. In this work, we report a density functional theory investigation of the structural, energetic, and electronic properties of binary 55-atom PtCo particles at a saturated CO atmosphere (31 molecules), i.e., (CO)₃₁/Pt_<i>n</i>Co_{55–<i>n</i>}. For PtCo in the gas phase, which adopts an icosahedron-like (ICO-like) structure in the lowest-energy configurations for all studied compositions, we found a rough correlation between stability and the number of bonds among the Pt and Co species; i.e., the stability (excess energy) increases (decreases) by increasing the number of Pt and Co bonds and with a minimum at about <i>n</i> = 28–42 (Pt-rich). However, at a saturated CO atmosphere, we found a stability displacement toward higher Co concentration (<i>n</i> = 6–20, Co-rich), which can be explained by the structural expansion of the nanocluster surface driven by the CO ligands. That is, the CO adsorption contributes to release the strain, which is induced by the attractive Coulomb interactions between the anionic surface and cationic core regions. Furthermore, for particular compositions (<i>n</i> = 42), we found a displacement of the Co atoms toward the surface upon the CO adsorption, which can be explained also by strain release as the adsorption energy of CO is larger on the Pt surfaces, which could favor Pt-rich surfaces