Chemical Physics最新文献

{"title":"A molecular dynamics study of NiO catalyst-induced perylene prenucleation","authors":"Dilfuza Husanova ,&nbsp;Kamoliddin Mehmonov ,&nbsp;Sirojiddin Mirzaev ,&nbsp;Umedjon Khalilov","doi":"10.1016/j.chemphys.2025.112891","DOIUrl":"10.1016/j.chemphys.2025.112891","url":null,"abstract":"<div><div>Organic nanocrystals (ONCs) are pivotal in optoelectronics due to their unique properties, yet the early stages of their formation, particularly their catalytic role in prenucleation, are unclear. This study uses molecular dynamics simulations to explore the effects of NiO nanoparticles (NPs) on the prenucleation of perylene-based ONCs, specifically PERLEN08 and RELVUC. Results show that NiO NPs significantly alter cluster formation rates and stability. The catalyst's presence introduces key kinetic, thermodynamic, and structural differences compared to the uncatalyzed system. PERLEN08 forms clusters faster than RELVUC in the presence of NiO, attributed to differing adsorption barriers from molecular structure and hydrogen bonding. NiO also enhances cluster stability for both systems. Structural analysis indicates predominantly amorphous pre-nucleation clusters, supporting non-classical nucleation mechanisms. By providing an atomic-scale mechanism for catalyst selectivity, these findings help interpret experimental results on substrate-dependent nucleation and provide a basis for the rational design of catalysts to control ONC synthesis.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"600 ","pages":"Article 112891"},"PeriodicalIF":2.4,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144830218","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":"Advancing perovskite solar cells: Inorganic CCTS hole-transporting material for enhanced efficiency and stability","authors":"Fahriye Sari ,&nbsp;Sultan Suleyman Ozel ,&nbsp;Adem Sarilmaz ,&nbsp;Faruk Ozel ,&nbsp;Mahmut Kus ,&nbsp;Mustafa Ersoz","doi":"10.1016/j.chemphys.2025.112889","DOIUrl":"10.1016/j.chemphys.2025.112889","url":null,"abstract":"<div><div>One of the most effective methods for generating renewable energy is the efficient conversion of photons into electrical energy using environmentally sustainable materials. In recent years, the integration of chalcogenide materials, which exhibit graphene-like semiconducting properties and high charge carrier mobility, into perovskite solar cells (PSCs) has garnered significant attention for enhancing the performance, stability, and eco-friendly nature of these devices. In this study, Cu₂CoSnS₄ (CCTS) nanocrystals were synthesized and utilized as a fully inorganic hole transport layer (HTL) in inverted PSCs. Devices incorporating 6 vol% CCTS achieved a power conversion efficiency (PCE) of 10.07 %, and retained 93 % of their initial efficiency after 720 h under inert storage conditions, without encapsulation. This demonstrates a notable improvement in stability compared to conventional PEDOT: PSS-based devices. The optimized CCTS HTL provided better energy level alignment, reduced moisture ingress, and enhanced charge transport. These findings indicate that CCTS is a promising inorganic HTL candidate for efficient and stable PSCs.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112889"},"PeriodicalIF":2.4,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826484","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":"First-principles study of ABSe₃ (A = Li, Na) Perselenoborates: A Promising Family of Nonlinear Optical Materials","authors":"Garadi Fatima ,&nbsp;Halit Mohamed ,&nbsp;Bourahla Saida ,&nbsp;Maabed Said ,&nbsp;Mebarki Hanifi ,&nbsp;Bouchenafa Mohamed ,&nbsp;Chérif F.Matta","doi":"10.1016/j.chemphys.2025.112886","DOIUrl":"10.1016/j.chemphys.2025.112886","url":null,"abstract":"<div><div>The properties of perselenoborates ABSe₃ (A = Li, Na) are investigated for the first time using density functional theory (DFT). These compounds crystallize in the orthorhombic system, adopting the <em>Pca</em>2₁ and <em>Pna</em>2₁ space groups for LiBSe₃ and NaBSe₃, respectively. A plane-wave pseudopotential (PW-PP) approach combined with the GGA-PBE functional employed to examine their structural, elastic, electronic, and optical properties. In parallel, the linear combination of atomic orbitals (LCAO) method used to explore the electronic band structure with GGA-PBE, HSE06, and B3LYP functionals, as well as the second harmonic generation (SHG) response using GGA-PBE.</div><div>The results reveal that both compounds are indirect semiconductors, with band gap values that vary depending on the functional used. The density of states (DOS) analysis confirms the covalent nature of the B<img>Se bonds. Optical calculations show significant birefringence in both materials, and the (BSe₄)⁵⁻ anionic units found to dominate the SHG response and birefringence, while the alkali metal cations have minimal influence. Mechanical analysis confirms the structural stability and elastic anisotropy of both phases. Thermal calculations indicate low thermal conductivity and relatively low melting points for LiBSe₃ and NaBSe₃, which may limit their use in high-temperature environments.</div><div>Overall, these findings suggest that LiBSe₃ and NaBSe₃ are promising candidates for nonlinear optical applications, particularly in frequency conversion and birefringent devices. Their combination of anisotropic optical response, semiconducting behavior, and low thermal conductivity supports their potential for integration into thermally sensitive photonic systems.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"600 ","pages":"Article 112886"},"PeriodicalIF":2.4,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144842028","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":"Influence of variable molecular diameters on vibrational–electronic state-specific transport coefficients","authors":"Istomin V.A.,&nbsp;Kustova E.V.","doi":"10.1016/j.chemphys.2025.112863","DOIUrl":"10.1016/j.chemphys.2025.112863","url":null,"abstract":"<div><div>Detailed vibrational–electronic and simplified electronic state-to-state approaches for transport properties of non-equilibrium high-temperature flows are developed using the generalized Chapman–Enskog method. The algorithm for the transport coefficients calculation takes into account variable collision diameters of excited species. Effective diameters of atoms and molecules in different electronic and vibrational states are evaluated using the Slater, Hirschfelder and Tietz-Hua models; the latter two models yield similar results for molecules at the ground electronic state. At temperatures above 10000 K, a noticeable effect of increasing collision diameters on the state-specific transport coefficients is found, especially in case of non-equilibrium distributions over internal states.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112863"},"PeriodicalIF":2.4,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144766816","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":"DFT and AIMD study of stability, electronic, magnetic, thermal, and optical properties of two-dimensional ZnX2 (X = Cl, Br and I) semiconductor","authors":"Saman Sarkawt Jaafar ,&nbsp;Dlear Rafiq Saber ,&nbsp;Nzar Rauf Abdullah","doi":"10.1016/j.chemphys.2025.112862","DOIUrl":"10.1016/j.chemphys.2025.112862","url":null,"abstract":"<div><div>This work examines the structural, electronic, magnetic, thermal, dynamic, and optical properties of two-dimensional (2D) ZnX<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> (X = Cl, Br, I) through density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The 2D ZnX<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> exhibits planar buckling in which ZnI<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> exhibits the highest degree of buckling, followed by ZnBr<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> and ZnCl<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>. Consequently, the highest buckling of ZnI<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> exhibits the narrowest band gap, while the lowest buckling structure of ZnCl<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> gives rise a widest band gap. This suggests that the electronic band gap is predominantly influenced by buckling in addition to electronegativity differences. Moreover, spin–orbit coupling (SOC) induces a reduction in the band gaps of these non-magnetic structures, primarily through the splitting and shifting of electronic states. Furthermore, stability assessments confirm that ZnX<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> structures are dynamically and thermally stable. In addition, thermal analysis reveals that ZnI<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> has the highest heat capacity, attributed to degenerate acoustic phonons. Finally, optical investigations indicate ZnI<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> absorbs light in the near-UV spectrum, while ZnCl<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> and ZnBr<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> absorb in the Mid-UV region. The planar buckling significantly influence the physical properties of ZnX<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> enhancing their suitability for advanced technological applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112862"},"PeriodicalIF":2.4,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144766815","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":"Unveiling the catalytic versatility of transition metal-doped coal char systems for hydrogen evolution reaction: a first-principles approach","authors":"Abosede Adejoke Badeji ,&nbsp;Kowthaman Pathmanathan ,&nbsp;Hewa Y. Abdullah ,&nbsp;Ismail Hossain ,&nbsp;Musa Runde","doi":"10.1016/j.chemphys.2025.112882","DOIUrl":"10.1016/j.chemphys.2025.112882","url":null,"abstract":"<div><div>Transition metal-doped engineered coal char (TM^dopChar) systems have emerged as exceptional electrocatalysts for hydrogen evolution reaction (HER), leveraging their tailored geometric, electronic, and quantum chemical properties. Short TM-H bond lengths (1.4–1.8 Å) promote efficient hydrogen adsorption and H<img>H coupling, while spin state adaptability enhances catalytic flexibility in systems like Sc^dopChar, Ti^dopChar, and Ni^dopChar. Quantum chemical analyses revealed that favorable low energy gaps (Eg) and HOMO-LUMO alignments in these systems drive superior catalytic performance. Adsorption and QTAIM studies demonstrated that H@Zn^dopChar exhibits optimal adsorption-desorption dynamics, with the lowest Gibbs free energy (ΔG_H) of 0.036 eV for the Tafel mechanism, outperforming established electrocatalysts in HER efficiency. The versatility of TM@Char systems is highlighted by their ability to balance strong covalent and non-covalent interactions, making them promising candidates for sustainable hydrogen production technologies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112882"},"PeriodicalIF":2.4,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756747","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":"Vacuum ultraviolet spectra of gas phase organophosphorus solvent for nuclear fuel applications: Di-(2-ethyl-hexyl) phosphoric acid","authors":"Tamaghna Maitra ,&nbsp;Param Jeet Singh ,&nbsp;Atanu Bhattacharya ,&nbsp;Suman Das ,&nbsp;K.K. Gorai ,&nbsp;D.V. Udupa","doi":"10.1016/j.chemphys.2025.112875","DOIUrl":"10.1016/j.chemphys.2025.112875","url":null,"abstract":"<div><div>Vacuum ultraviolet (VUV) spectra of an important organophosphorus based solvent DI (2- Ethyl hexyl) phosphoric acid abbreviated as D2EHPA in the gaseous phase are reported within the wavelength range of 130–190 nm at different base pressure levels utilizing a synchrotron source at room temperature. The analysis of the experimental photo absorption spectra is further complemented with theoretical analysis comprising of density functional theory and molecular dynamics simulations. The theoretical analysis confirms the nature of electronic transitions to be of charge transfer type or a mixture of charge transfer and local excitation type.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112875"},"PeriodicalIF":2.4,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144739549","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 theoretical study on the interaction of orthosilicic acid with water molecules","authors":"I.K. Petrushenko ,&nbsp;Bapan Saha","doi":"10.1016/j.chemphys.2025.112876","DOIUrl":"10.1016/j.chemphys.2025.112876","url":null,"abstract":"<div><div>Understanding the physico-chemical properties of water/silica interfaces is of key importance in different fields. In view of this, the interactions of water molecules, [(H₂O)_n, <em>n</em> = 1–4], with an orthosilicic acid cluster, [Si(OH)₄], has been studied by several theoretical methods. These interactions are found to be stable and increase with the increase in the number of interacting water molecules. SAPT0 calculations on the adducts has suggested that the sequential adsorption of H₂O molecules on the cluster is primarily electrostatic (up to 70 %) followed by induction interactions (∼18–20 %). The dispersion component contributes moderately (∼ 10–15 %) to the stability of these interactions. The IGM analysis has revealed the simultaneous involvement of hydrogen bonding and van der Waals interactions between water molecules and the Si(OH)₄ cluster. The use of the AIMD technique has suggested the stability of water/Si(OH)₄ clusters at room temperature.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112876"},"PeriodicalIF":2.4,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144723139","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":"HSE03 functional-based DFT screening the multifaceted properties of inorganic halide perovskites ABI3 (a = ca, Ba; BK, Rb) for cutting-edge optoelectronic applications","authors":"Muhammad Riaz ,&nbsp;Muhammad Waqas Mukhtar ,&nbsp;Syed Mansoor Ali ,&nbsp;Muhammad Imran Saleem ,&nbsp;Rajeh Alotaibi","doi":"10.1016/j.chemphys.2025.112881","DOIUrl":"10.1016/j.chemphys.2025.112881","url":null,"abstract":"<div><div>Halide perovskites have gained immensive focus in diverse scientific and technological domains because of their inherent structural flexibility. Herein, first-principles calculations were carried out within the CASTEP framework using the HSE03 hybrid functional to investigate the structural, electronic, elastic, bond population, and optical properties of ABI₃ (A = Ca, Ba; B = K, Rb) inorganic halide perovskites. All compounds exhibit semiconducting behavior with band gap values of 2.07 eV for CaKI₃, 1.63 eV for CaRbI₃, 0.936 eV for BaKI₃, and 3.202 eV for BaRbI₃, while their negative formation energies and phonon dispersion spectra further support the dynamic stability. However, CaKI₃ stand out promising candidate based on its favorable dielectric function, high absorption coefficient, and strong optical conductivity. Moreover, mechanically derived parameters from elastic constants (C₁₁, C₁₂, and C₄₄) indicate the mechanical stability and ductility, as demonstrated by their Poisson's ratios (&gt;0.25), Pugh's ratios (&gt;1.75), and adherence with Born criteria. These results suggested that considered ABI₃ (A = Ca, Ba; B = K, Rb) inorganic halide perovskite hold significant potential for modern optoelectronics applications.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112881"},"PeriodicalIF":2.4,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144739561","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":"Study on thermal decomposition and combustion mechanism of azobisisobutyronitrile: Combined with TG-DSC-FTIR-GC-MS technology and the ReaxFF molecular dynamics","authors":"Jinkun Liu ,&nbsp;Zhanfang Liu ,&nbsp;Jun Zhu ,&nbsp;Guannan Zhang ,&nbsp;Yajun Li ,&nbsp;Zhenwen Sun ,&nbsp;Hong Zhou ,&nbsp;Zheng Zhou ,&nbsp;Xianhe Deng ,&nbsp;Yao Liu","doi":"10.1016/j.chemphys.2025.112880","DOIUrl":"10.1016/j.chemphys.2025.112880","url":null,"abstract":"<div><div>As a typical energetic initiator, the pyrolysis and combustion mechanisms of azobisisobutyronitrile (AIBN) are of great significance for chemical safety and fire/explosion accidents investigation. Addressing the challenge that traditional experimental methods struggle to fully detect intermediates and final products, this study reveals the thermal behavior characteristics of AIBN via TG-DSC-FTIR-GC–MS technology. A significant phenomenon of coupled melting and decomposition was observed. Pyrolysis products such as nitrogen, carbon monoxide, acetic acid, methacrylonitrile, isobutyronitrile, and tetramethylsuccinonitrile were identified. By integrating molecular dynamics with ReaxFF force field, the micro-reaction pathways and product formation mechanisms were analyzed. The reliability of the simulation method was verified by comparing the activation energy (<em>E</em>_a) calculated from DSC with simulated values. The effects of different temperatures (2000–3500 K) and O₂ atmosphere on the initial decomposition, major products, and reaction pathways of AIBN were investigated. Results show that the initial decomposition during pyrolysis is primarily initiated by the N-containing radical C₄H₆N, while the combustion process is driven by oxygen-containing radicals. The participation of oxygen significantly alters the reaction pathways, with O₂-involved reactions accounting for 84.7 % at 2000 K. Furthermore, the formation and decomposition pathways of products such as CO, CO₂, H₂, H₂O, and HCN were clarified, and a complete reaction network for AIBN pyrolysis and combustion was constructed. The mutual validation between experimentally detected products and simulated pathways provides a new experimental-simulation integrated approach for thermal safety assessment and explosion mechanism research of azo-based hazardous chemicals.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"599 ","pages":"Article 112880"},"PeriodicalIF":2.0,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144711684","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}