Physical Chemistry Chemical Physics最新文献

{"title":"An In-Depth Investigation of Lead-FreeKGeCl3Perovskite Solar Cells Employing Optoelectronic, Thermomechanical and Photovoltaic Properties: DFT and SCAPS-1D Frameworks","authors":"Md. Tarekuzzaman, Mohammad Hasin Ishraq, Md. Shahazan Parves, M. A. Rayhan, Sohail Ahmad, Md. Rasheduzzaman, K. A. Al Mamun, M. Moazzam Hossen, Md. Zahid Hasan","doi":"10.1039/d4cp02974g","DOIUrl":"https://doi.org/10.1039/d4cp02974g","url":null,"abstract":"Potassium Germanium Chloride (KGeCl3) emerges as a promising contender as an absorber material for lead-free perovskite solar cells (PSCs), offering significant potential and competitiveness in this domain. Nevertheless, KGeCl3-based PSCs are still striving to attain the exceptional performance levels demonstrated by hybrid PSCs. In this study, we conducted a density functional theory (DFT) investigation employing the Cambridge Serial Total Energy Package (CASTEP) code to analyze and assess the structural, electronic, mechanical, and optical characteristics of the cubic KGeCl3 absorber. The positive phonon dispersion curve confirms the dynamical stability of KGeCl3. The elastic constant satisfied the Born criteria, validating the mechanical stability and ductility of solid KGeCl3. The electronic band structure and density of states (DOS) affirmed that the KGeCl3 material is a semiconductor with a direct band gap of 0.754 eV. The study also identified key parameters of optical properties such as absorption, conductivity, reflectivity, dielectric function, refractive index, and loss function. These optical findings reveal the potential suitability of our compound KGeCl3 for solar applications. The Helmholtz free energy (F), internal energy (E), entropy (S), and specific heat capacity (Cv) are computed based on the phonon density of states. Additionally, we investigated twenty-four configurations comprising different combinations of electron transport layers (ETLs) and hole transport layers (HTLs) in SCAPS-1D software. For this purpose, ETLs such as Ws2, ZnSe, PCBM, C60 are utilized, while HTLs including CBTS, CdTe, CFTS, Cu2O, P3HT, PEDOT: PSS are employed. The highlighted structure, ITO/CBTS/ KGeCl3/Ws2/Ni, demonstrates remarkable performance with an efficiency of 22.01%, Voc of 0.6799 V, Jsc of 41.439 mA/cm2, FF of 78.12 %. To analyze Photovoltaic (PV) performance, we chose the top four solar cell (SC) configurations. Moreover, a comprehensive examination was conducted to assess the impact of various factors, including the thickness of different layers, capacitance, Mott-Schottky, series and shunt resistance, temperature, and generation-recombination rates, as well as J-V (current-voltage density) and quantum efficiency (QE) characteristics. These results are meticulously situated within existing research, demonstrating the study’s impact on non-toxic, inorganic perovskite solar technology.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effect of hydrogen bonding on the π depletion and the π − π stacking interaction","authors":"Dage Sundholm, Usman Ahmed, Mikael P. Johansson","doi":"10.1039/d4cp02889a","DOIUrl":"https://doi.org/10.1039/d4cp02889a","url":null,"abstract":"Non-covalent interactions such as hydrogen bonding and π-π stacking are very important type of interactions governing molecular self-assembly. The π-π stacking ability of aromatic rings depends on the electron density of the π orbitals, which is affected by the electron-withdrawing or electron-donating properties of the substituents. We have here studied the effect of hydrogen bonding on the strength of the π-π stacking interactions by calculating the binding energies at the explicit correlated Møller-Plesset (MP2-F12) perturbation theory level using triple-ζ polarization quality basis sets. The stacking interactions in the presence of hydrogen bonding are found to be stronger than in the absence of the hydrogen bonding suggesting that hydrogen bonds lead to π depletion, which affects the aromatic character of the aromatic rings and increases the strength of the π-π stacking interaction. We have also studied how hydrogen bonding affects the stacking interaction by calculating local orbital locator integrated pi over plane (LOLIPOP) indices. Comparing LOLIPOP indices with the stacking-interaction energies calculated at the MP2-F12 level shows that there is no clear correlation between the stacking-interaction energies and LOLIPOP indices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic insights into the electron attachment process to guanosine in the presence of arginine","authors":"Manash Pratim Sarmah, Manabendra Sarma","doi":"10.1039/d4cp02558j","DOIUrl":"https://doi.org/10.1039/d4cp02558j","url":null,"abstract":"The attachment of low-energy electrons (LEEs) to the DNA biomolecules leads to irreversible damage. However, the behavior of this interaction can be influenced by the presence of amino acids. Herein, we have delved into the mechanism of electron attachment to the guanosine in the presence of arginine. The study used combined molecular dynamics (MD) simulations and quantum mechanics/molecular mechanics (QM/MM) approaches to collect and optimize the geometries having hydrogen-bonds (H-bonds) between guanosine and arginine, respectively, followed by atom centered density matrix propagation (ADMP) simulations to assess the electron attachment ability of guanine with and without arginine. The vertical detachment energy (VDE) and natural population analysis (NPA) suggest that the electron attached to guanosine is more readily due to the H-bonds between guanosine and arginine. The singly occupied molecular orbitals (SOMOs), VDE, and NPA from ADMP results corroborated the idea that in the presence of arginine electron effectively attached to guanosine moiety while the auto detachment process becomes less probable in the case of arg-guanosine (two-H bonds). However, in the presence of arginine, the dissociative electron attachment (DEA) process for guanosine is exothermic, while in the absence of arginine, it is endothermic. This study provides new insight into the process of radiation damaging biological systems by elucidating the DEA to DNA subunits in the presence of amino acids, paving the way for a deeper understanding of radiation-induced damage in biological systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Participation of Transition Metal Atoms in Noncovalent Bonds","authors":"Steve Scheiner","doi":"10.1039/d4cp03716b","DOIUrl":"https://doi.org/10.1039/d4cp03716b","url":null,"abstract":"The existence of halogen, chalcogen, pnicogen, and tetrel bonds as variants of noncovalent σ and π-hole bonds is now widely accepted, and their properties have been elucidated. The ability of the d-block transition metals to potentially act as Lewis acids in a similar capacity is examined systematically by DFT calculations. Metals examined span the entire range of the d-block from Group 3 to 12, and are selected from several rows of the periodic table. These atoms are placed in a variety of neutral MXn molecules, with X = Cl and O, and paired with a NH3 nucleophile. The resulting M··N bonds tend to be stronger than their p-block analogues, many of them with a substantial degree of covalency. The way in which the properties of these bonds is affected by the row and column of the periodic table from which the M atom is drawn, and the number and nature of ligands, is elucidated.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comparing coupled cluster and composite quantum chemical methods for computing activation energies and reaction enthalpies of radical propagation reactions","authors":"Timothy B. Huber, Ralph A. Wheeler","doi":"10.1039/d4cp03676j","DOIUrl":"https://doi.org/10.1039/d4cp03676j","url":null,"abstract":"Accurate determination of activation energies and reaction enthalpies is essential for understanding the propagation step in free radical polymerization, as it significantly affects polymer chain length and structure. In this study, we compare DLPNO-CCSD(T) to canonical CCSD(T) for 17 radical addition activation energies and 18 reaction enthalpies from Radom and Fischer’s test set. Additionally, we compare the computationally efficient composite methods G3(MP2)-RAD and CBS-RAD against CCSD(T)/aug-cc-pVTZ and DLPNO-CCSD(T)/CBS methods. Compared to the CCSD(T)/aug-cc-pVTZ reference, our results indicate that DLPNO-CCSD(T)/CBS with unrestricted Hartree-Fock (UHF) or UB3LYP reference orbitals and NormalPNO parameters consistently achieves chemical accuracy, with mean absolute deviations of 3.5 kJ/mol for activation energies and 1.5 kJ/mol for reaction enthalpies. Comparing the two composite methods shows that CBS-RAD agrees most closely with coupled cluster reaction enthalpies, while G3(MP2)-RAD tracks the activation energies most closely.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449889","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A variational method for studying the photodissociation of triatomic molecules","authors":"Marco Pezzella, Georgi Mitev, Sergey N Yurchenko, Jonathan Tennyson, Alexander Mitrushchenkov","doi":"10.1039/d4cp02771j","DOIUrl":"https://doi.org/10.1039/d4cp02771j","url":null,"abstract":"The photodissociation of molecules is becoming an increasingly important factor to consider in the evolution of exoplanets' atmospheres orbiting around UV-rich stars, as it leads to the enrichment of atmospheric complexity. A new method has been developed for computing the rotationally and vibrationally resolved photodissociation spectrum of triatomic molecules. The time-independent Schr\"{o}dinger equation is solved using the variational nuclear motion program textsc{Everest}; textsc{Exocross} is employed to compute the cross sections by applying Gaussian smoothing to a the set of discrete transitions into the continuum. HCN is chosen as the test molecule, as it has been widely studied in the literature. Results are compared with the available experiments. The temperature dependence is explored for temperatures up to 3000 K.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cation Effects and Charge Inversion Contribute to the Electrostatic Stabilisation of Protein Bioconjugates in Neat Ionic Liquids","authors":"Lokesh Soni, Raj Kumar, Kamendra P. Sharma, Ajay Singh Panwar","doi":"10.1039/d4cp01811g","DOIUrl":"https://doi.org/10.1039/d4cp01811g","url":null,"abstract":"Dispersing and stabilising proteins in ionic liquids (ILs) provides significant opportunities for green solvent-based biocatalysis, especially in industrial processes at elevated temperatures. While unmodified proteins undergo denaturation, their polymer-conjugated counterparts have been stabilised in neat ILs. However, the nature of interactions and the generality of protein-bioconjugates stabilisation in neat ILs requires further understanding.Using a combination of different physio-chemical experimental tools and molecular dynamics (MD) simulations, here we investigate the dispersion and driving force for the stabilisation of bioconjugates in neat ILs. Solvent-free bioconjugates of different proteins viz. myoglobin, α-chymotrypsin, and regenerated silk fibroin having predominant α-helical, β-sheet, and random coiled secondary structures, respectively, were prepared by electrostatic coupling with polyethylene-glycol (PEG)-based polymer-surfactant (PS). Protic IL (PIL, N-methyl-2-pyrolidonium trifluoromethane sulfonate; [NMP][OTF]) and aprotic ionic liquid (AIL, 1-methyl-3-(4-sulfobutyl)-1H-imidazol-3-ium trifluoromethane sulfonate; [MEZ][OTF]) were synthesized to study the bioconjugate dispersion. Interestingly, time-dependent polarised optical microscopy combined with transmittance measurements showed complete dispersion of all bioconjugates only in AIL. MD simulations of PS-cCT bioconjugate were carried out in the same ILs as the experiments. The surface electrostatic potential of PS-cCT reversed from positive in PIL to negative in AIL due to overcharging by AIL anion and lower mobility of AIL cation. Strong screening of electrostatic potentials between two PS-cCT complexes in PIL resulted in reduced dispersion stability. Lower diffusivity of long alkyl chain [MEZ] cations of AIL lead to a depletion zone of IL ions between two PS-cCT complexes (separation < 70Å), thus resulting in a significant negative potential between the complexes. Hence, protein bioconjugates in AIL were stabilised by a combination of surface overcharging and steric exclusion of [MEZ] cations from the space between approaching bioconjugate complexes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxidation of fine aluminum particles: thermal-induced transformations in particle shells and kinetics of oxide nucleation","authors":"Andrey V. Korshunov","doi":"10.1039/d4cp03355h","DOIUrl":"https://doi.org/10.1039/d4cp03355h","url":null,"abstract":"The paper investigates the process of oxidation of fine aluminum powder, consisting of spherical Al particles of a ‘metal core/oxide shell’ type, when heated in air at temperatures below 550°C. The highly dispersed aluminum powder ‘Alex' used in the work (particle size 0.05-1.5 μm, average numerical particle diameter DN = 0.11 μm) was produced by electric explosion of a thin Al wire in argon with subsequent passivation in an oxygen-containing atmosphere. For the first time, the influence of particle size on the oxidation process has been identified. During the reaction, individual γ-Al2O3 oxide nuclei grow at the surface of Al particles with diameters less than 300 nm without laterally overlapping to form a protective passivating layer, as typically occurs during the oxidation of micron-sized particles or bulk metal. The localization of γ-Al2O3 nuclei is determined by the regions of peeling off the primary amorphous oxide film from the surface of the metal core of an Al particle due to the thermal decomposition of aluminum hydroxides (T350C) present within the particle shells. A significant increase in the contributions of the following factors leads to a high oxidation rate: the diffusion within disordered structure of a particle core and the surface diffusion of cations (Еа = 80.65.3 kJ/mol, 400–450°C), the surface and grain boundary diffusion of oxygen during the growth of γ-Al2O3 crystallites (Еа = 108.311.2 kJ/mol, 470–500°C) and the surface and grain boundary transport of anions through an amorphous and underling nanocrystalline oxide layer with a constant thickness (Еа = 205.18.6 kJ/mol, 520–550°C). The results obtained make it possible to expand the theoretical understanding of the manifestations of the size effect in solid-phase reactions and take into account its influence in practice.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Densification of Sodium and Magnesium Aluminosilicate Glasses at Ambient Temperature: Structural Investigations by Solid-state Nuclear Magnetic Resonance and Molecular Dynamics Simulations","authors":"Millena Logrado, Yara Hellen Firmo Gomes, Tomiki Inoue, Shingo Nakane, Yoshinari Kato, Hiroki Yamazaki, Akihito Yamada, Hellmut Eckert","doi":"10.1039/d4cp02431a","DOIUrl":"https://doi.org/10.1039/d4cp02431a","url":null,"abstract":"Sodium and magnesium aluminosilicate glasses with compositions 20Na2O-20Al2O3-60SiO2 (NAS) and 20MgO-20Al2O3-60SiO2 (MAS) were subjected to a 12 and 25 GPa compression and decompression at room temperature, resulting in density increases from 3.7 % to 5.3 % (NAS) and from 8.2 to 8.4 % (MAS), respectively. The pressurization at 25 GPa was done on 17O enriched glasses, to facilitate characterization by 17O NMR. The structural changes associated with this process have been investigated by solid state 29Si, 27Al, 23Na, 25Mg, and 17O magic-angle spinning (MAS)-NMR and compared with the situation in thermally relaxed glasses and/or glasses prepared at ambient pressure. While in the Na aluminosilicate glass only subtle structural changes are observed in a sample densified at 12 GPa, the average coordination number of Al <CN(Al> increases moderately from 4.00 to 4.26 by pressurization at 25 GPa. In the Mg-based system, <CN(Al> increases from 4.34 to 4.57 to 4.83 in the sequence 10-4 GPa -> 12 GPa -> 25 GPa. The experimental result at 25 GPa was qualitatively confirmed by Molecular Dynamics (MD) simulations. Overall, pressurization results in more positive 29Si and 17O chemical shifts, most likely reflecting a reduction in the Si-O-Si and Si-O-Al bonding angles in the pressurized glasses. Furthermore, the results are also consistent with either an increased number of non-bridging O-atoms upon pressurization, or a larger number of Si-O-Al or Al-O-Al linkages. The significantly higher sensitivity of MAS, compared to NAS glass, to an increase in <CN(Al> upon pressurization provides a good structural rationale for their significantly higher crack initiation resistances.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142443881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tunable valley polarization and high Curie temperature in two-dimensional GdF2/WSe2 van der Waals heterojunction","authors":"Xu Zhang, Kai Zhang, Yadong Zhu, Baozeng Zhou, X. C. Wang","doi":"10.1039/d4cp03578j","DOIUrl":"https://doi.org/10.1039/d4cp03578j","url":null,"abstract":"Two-dimensional (2D) van der Waals (vdW) heterojunction have potential applications in spintronic devices owing to their unique electronic structure and properties. The 2D ferromagnetic material GdF2 formed by rare earth element (Gd) with 4f electron and fluorine has spontaneous valley polarization, perpendicular magnetic anisotropy and other excellent properties. The monolayer WSe2 has a similar structure to the monolayer GdF2, can be used to construct vdW heterojunction. The heterojunction not only retain the original excellent properties, but also generating new physical properties due to interfacial charge transfer and coupling. Therefore, this work studies the electronic structure, magnetic anisotropy energy and Curie temperature (Tc) of GdF2/WSe2 heterojunction. The GdF2/WSe2 heterojunction exhibits spontaneous valley polarization, and can be modulated by biaxial strain. Addition, the valley polarization can be regulated by applying external electric field and changing interface spacing. These results indicate that GdF2/WSe2 heterojunction can be used as promising platforms for the study of spintronics and valleytronic devices, and provide ideas for the development of new electronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":3.3,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}