Chemical Physics最新文献

{"title":"Novel multi-spray approach for preparing Cu₂ZnSnS₄ films for efficient solar photoelectrochemical water splitting","authors":"Ahmed Saoudi ,&nbsp;Yazid Bouznit ,&nbsp;Fathi Chouikh ,&nbsp;Gerard Leroy","doi":"10.1016/j.chemphys.2025.112894","DOIUrl":"10.1016/j.chemphys.2025.112894","url":null,"abstract":"<div><div>In this paper, a novel multi-spray approach was adopted and optimized to prepare high quality Cu₂ZnSnS₄ films. To achieve the Cu₂ZnSnS₄ phase under optimized conditions using this technique, a series of samples with different Cu:Zn:Sn:S atomic ratios were prepared and investigated using various characterization methods. X-ray diffraction (XRD) analysis indicated that the crystalline quality was strongly dependent on the Cu:Zn:Sn:S atomic ratios. In all cases, a pure Cu₂ZnSnS₄ kesterite phase structure with (112) orientation was obtained. All prepared films exhibited low transmittance (approximately 30 %) in the visible region. Electrochemical photocurrent tests showed that the films presented a cathodic photocurrent, thus confirming the p-type conductivity of the prepared films. Films deposited using a solution with the stoichiometric composition (Cu₂ZnSnS₄) exhibited excellent structural, morphological and electrochemical properties, with photocurrent density reaching up to 6 mA/cm².</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"600 ","pages":"Article 112894"},"PeriodicalIF":2.4,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144860676","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 calculations of the mechanical, electronic, vibrational, and thermodynamic properties of bis(2,4,6-trinitrophenyl) ether","authors":"Hao Liu ,&nbsp;Wei Zeng ,&nbsp;Zheng-Tang Liu ,&nbsp;Xiang-Hui Chang","doi":"10.1016/j.chemphys.2025.112896","DOIUrl":"10.1016/j.chemphys.2025.112896","url":null,"abstract":"<div><div>A systematic study was conducted using density functional theory (DFT) on the recently synthesized high-energy explosive bis (2,4,6-trinitrophenyl) ether (BTNPE) to elucidate its mechanical, electronic, vibrational, and thermal properties. The calculation method adopts Perdew Burke Ernzerhof (PBE) generalized gradient approximation (GGA) with Grimme DFT-D dispersion correction. The deviation between optimized lattice parameters and experimental crystallographic data is less than 2.6 %, while the error in volume is 3.52 %. Electronic structure analysis revealed an indirect bandgap of 2.596 eV, while phonon dispersion and density of states confirmed the dynamic stability of covalently bonded crystals, and vibrational spectroscopy (IR/Raman) determined characteristic functional group modes. The thermodynamic functions derived from quasi harmonic approximation exhibit temperature dependence. These results provide fundamental insights for future experimental validation and high-energy material design.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"600 ","pages":"Article 112896"},"PeriodicalIF":2.4,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144841543","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":"Effects of different directions and intensities of external electric fields on the dissociation and excitation characteristics of meta‑bromine-nitrobenzene and 5‑bromine-2-fluoro-nitrobenzene molecules","authors":"Chen Qin ,&nbsp;Yi Li ,&nbsp;Min Zhang ,&nbsp;Jianxin Liu ,&nbsp;Jinquan Chen","doi":"10.1016/j.chemphys.2025.112892","DOIUrl":"10.1016/j.chemphys.2025.112892","url":null,"abstract":"<div><div>This study investigates the dissociation and excitation properties of <em>meta</em>-bromonitrobenzene (mBNB) and 5-bromo-2-fluoronitrobenzene (5Br2FNB) under different orientation (C<img>Br or C<img>N bond axis) and intensity (0–0.035 a.u.) external electric fields (EEFs) using density functional theory at B3LYP/6-31+G(d,p) and ωB97XD/def2-TZVP levels. Results show that EEFs along the C<img>Br direction induce C<img>Br bond elongation, electron redistribution from NO₂ to Br, increased dipole moment, and weakened molecular stability. C<img>Br bond dissociation occurs at EEF strengths &gt;0.030 a.u., accompanied by a transition of the S₀ → S₁ excitation from n → π* localized excitation to Rydberg excitation with π → p_x feature. In contrast, EEFs along the C<img>N direction shorten C<img>Br bond, without promoting dissociation. The S₀ → S₁ excitation under C<img>N EEFs shifts from n → π* localized excitation to π → π* charge transfer. Fluorine substitution in 5Br2FNB exhibits limited influence on dissociation or excitation compared to mBNB. These findings demonstrate that directionally applied EEFs effectively modulate molecular stability and dissociation pathways, with C<img>Br-oriented EEFs facilitating environmentally relevant Br elimination.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"600 ","pages":"Article 112892"},"PeriodicalIF":2.4,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144860679","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 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}