Chemical Physics最新文献

{"title":"First-principles calculations to Investigate structural, Electronic, Optoelectronic, and Thermoelectric properties of HfRhP half-Heusler compound","authors":"M.K. Bamgbose ,&nbsp;G.T. Solola ,&nbsp;O.I. Atobatele ,&nbsp;C.O. Ilabija ,&nbsp;J.M. Whetode ,&nbsp;K.A. Ogunmoye","doi":"10.1016/j.chemphys.2025.113023","DOIUrl":"10.1016/j.chemphys.2025.113023","url":null,"abstract":"<div><div>The significant waste heat released from daily fossil fuel combustion contributes to global warming, which thereby necessitates direct waste heat-to-electricity conversion. This work presents a comprehensive first-principles investigation of the electronic, optoelectronic, and thermoelectric properties of the HfRhP half-Heusler compound for efficient energy harvesting. The investigation employed Density Functional Theory within the Generalized Gradient Approximation using the Perdew–Burke–Ernzerhof exchange–correlation functional. The calculations confirm the <span><math><mi>γ</mi></math></span> phase of HfRhP as the most energetically stable, with an equilibrium lattice parameter of <span><math><mrow><mn>5</mn><mo>.</mo><mn>93</mn><mtext>Å</mtext></mrow></math></span> and a direct band gap of <span><math><mrow><mn>0</mn><mo>.</mo><mn>89</mn><mtext>eV</mtext></mrow></math></span>. From the elastic constants and moduli, HfRhP is found to be ductile and highly resistant to linear compression. HfRhP is mechanically and thermodynamically stable. Seebeck coefficient of HfRhP is <span><math><mrow><mn>531</mn><mo>.</mo><mn>6</mn><mtext></mtext><mi>μ</mi><mtext>V/K</mtext></mrow></math></span> and figure of merit (<span><math><mrow><mi>Z</mi><mi>T</mi></mrow></math></span>) is 0.78. HfRhP has a high absorption coefficient and strong interband transition. These results reveal that HfRhP is high performance thermoelectric and optoelectronic candidate.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113023"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576682","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":"Comprehensive analysis of half-metallic, mechanical, electronic, thermodynamic, and optical properties of single perovskites LiCrZ3 (Z = Cl, Br, I)","authors":"Evren Görkem Özdemir ,&nbsp;Wisam Ayad Ahmed Ahmed","doi":"10.1016/j.chemphys.2025.113022","DOIUrl":"10.1016/j.chemphys.2025.113022","url":null,"abstract":"<div><div>The ferromagnetic phases of LiCrZ₃ (Z = Cl, Br, I) single perovskites are the most stable magnetic phases. Each single perovskite was obtained as an elastically stable material, and each material was ductile. The total magnetic moment values were obtained as 4.00 μ_B/f.u. for LiCrZ₃. The most partial contributions in each group came from Cr-transition metals. LiCrZ₃ materials exhibit a true half-metallic nature, displaying metallic behavior in up-spin orientations and semiconducting behavior in down-spin orientations. Thermodynamic calculations depending on temperature and pressure have been performed. The results of structural, electronic, elastic, and thermodynamic calculations, such as volume, Debye temperatures, and bulk modulus, are consistent. Heat capacity values take their constant values after 300 K for LiCrCl₃. While the remarkable electronic, magnetic, elastic, and thermodynamic properties of LiCrZ₃ (Z = Cl, Br, I) single perovskites make them suitable for spintronic technologies, their optical properties will also guide their use in optoelectronic technologies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113022"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576683","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":"Cooperative and stabilization effects in hydrogen-bonded chains of microhydrated thymine: a QTAIM and TD-DFT study","authors":"Murillo H. Queiroz ,&nbsp;Tiago V. Alves ,&nbsp;Roberto Rivelino","doi":"10.1016/j.chemphys.2025.112976","DOIUrl":"10.1016/j.chemphys.2025.112976","url":null,"abstract":"<div><div>We investigate the thresholds of the cooperative effects in hydrogen-bonded chains formed by thymine with 1 to 6 explicit water molecules. Using Density Functional Theory (DFT), combined with Quantum Theory of Atoms in Molecules (QTAIM) and Time-Dependent DFT (TD-DFT), we analyze the evolution of the electronic density at H-bond critical points (ρ H-bond) and its influence on the excited states. Our results indicate that the cooperative effect is stronger with the first water molecules, followed by weaker contributions beyond four water molecules. TD-DFT calculations reveal corresponding shifts in electronic transitions, linking H-bond topology with spectral changes. These findings contribute to a quantitative understanding of hydration effects in nucleobases, with implications for DNA stability and photochemistry.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112976"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340413","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":"Understanding the structures and dynamics of protic [EtNH3][NO3] and aprotic [Emim][NTF₂] ionic liquid mixtures from molecular dynamics simulation","authors":"Wenshu Liang,&nbsp;Dong Wang,&nbsp;Jia-ni Fan,&nbsp;Guangli Zhou,&nbsp;Qiying Xia,&nbsp;Xia Leng,&nbsp;Yunzhi Li","doi":"10.1016/j.chemphys.2025.113020","DOIUrl":"10.1016/j.chemphys.2025.113020","url":null,"abstract":"<div><div>The density, structures, dynamical properties and hydrogen bond (HB) dynamics of protic [EtNH₃][NO₃] and aprotic [Emim][NTF₂] ionic liquid mixtures forming {[Emim][NTF₂]}_x{[EtNH₃][NO₃]}_(1-x) with the molar fraction x = 0.00, 0.25, 0.50, 0.75 and 1.00 have been systematically investigated by using molecular dynamics simulations and a series of ab initio calculations. Our simulation results demonstrate that the studied IL mixtures is a quasi-ideal system, where two positive deviations (x = 0.25 and 0.50) and one negative deviation (x = 0.75) of the excess molar volume are less than 0.18 cm³·mol⁻¹. Further analysis indicates that the translational as well as rotational motions of [Emim]⁺ and [NTF₂]⁻ are restricted significantly with the decreasing the molar fractions. However, for [EtNH₃]⁺ and [NO₃]⁻, they display similar restrictions with the increasing the molar fractions in IL mixtures. Such restrictions can be attributed to the enhanced HB dynamics between [EtNH₃]⁺ and [NO₃]⁻ in the IL mixtures. Moreover, the HB strength of [Emim]⁺-[NTF₂]⁻ is enhanced with decreasing molar fractions in the IL mixtures, which can be better explained by the slower translational and rotational motions for [Emim]⁺ and [NTF₂]⁻ ions. More importantly, the binding energies for above cations and anions ion-pairs were determined by the ab initio calculations, which are in accordance with the MD simulation results. Our simulation results provide a molecular-level understanding the structures and dynamics of protic [EtNH₃][NO₃] and aprotic [Emim][NTF₂] ionic liquid mixtures, and will be a bit favorable to design and synthesis IL mixtures with specific properties.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113020"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145526350","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 ga-doped γ-TiAl intermetallic compound","authors":"Hongsheng Zhao ,&nbsp;Yuhao Chen ,&nbsp;Bingyin Feng ,&nbsp;Xubiao Wang ,&nbsp;Xiliang Zhang ,&nbsp;Qian Yang ,&nbsp;Jing Zhao ,&nbsp;Yinfeng Li ,&nbsp;Yanhui Wang","doi":"10.1016/j.chemphys.2025.112979","DOIUrl":"10.1016/j.chemphys.2025.112979","url":null,"abstract":"<div><div>TiAl-based alloys show great potential for aerospace and automotive applications but are limited by room-temperature brittleness and insufficient high-temperature strength. This study employs first-principles calculations to systematically investigate the effects of Ga doping at different sites (Ti substitution, Al substitution, and interstitial positions) on the structural, electronic, thermodynamic, and mechanical properties of γ-TiAl alloys. Results reveal that Ti-site substitution induces in-plane lattice contraction with c-axis expansion, while interstitial doping causes significant volumetric expansion. Electronic structure analysis shows that interstitial doping increases the density of states near the Fermi level, enhancing electron mobility, whereas Ti-site substitution strengthens bonding through enhanced d-d orbital hybridization. Al-site substitution exhibits the lowest thermal expansion coefficient (18 % reduction at 300 K), improving dimensional stability, while Ti-site substitution displays higher work functions (4.05–4.15 eV), suggesting better corrosion resistance. Mechanical properties are optimized at 0.03 % Ga concentration, at which the elastic modulus peaks at 194.48 GPa and the Pugh ratio (B/G = 1.75) indicates improved ductility. However, higher concentrations (≥0.04 %) lead to hardness reduction and increased elastic anisotropy. This work provides theoretical insights for optimizing TiAl alloys through controlled Ga doping strategies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112979"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425057","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":"Field-free orientation of LiH molecules controlled by a train of few-cycle/single-cycle terahertz laser pulses","authors":"Yuemin Leng,&nbsp;Wenqian Li,&nbsp;Yaoyao Wei,&nbsp;Shou Chai,&nbsp;Gaoren Wang,&nbsp;Yongchang Han,&nbsp;Jie Yu","doi":"10.1016/j.chemphys.2025.113003","DOIUrl":"10.1016/j.chemphys.2025.113003","url":null,"abstract":"<div><div>In recent years, how to enhance the effect of field-free orientation has attracted the attention of many researchers. Here, we propose a scheme for generating field-free orientation of LiH molecules using a train of few-cycle/single-cycle terahertz pulses. Theoretical calculations indicate that the field-free orientation degree of LiH molecules gradually increases with the number of laser pulses. After the interaction with five terahertz laser pulses, the maximum field-free orientation degree of molecules reaches 0.8568. Under this condition, the duration during which the field-free orientation degree remains above 0.5 is 161.8 fs, which is sufficient for experimental utilization. When the temperature is below 20 K, the molecules orientation degree remains above 0.5. By sequentially discussing the relationship between the time delay of adjacent pulses and the rotational state population, we uncovered the control mechanism of the proposed scheme. Additionally, we examined the laser-pulse-induced changes in their angular distribution.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113003"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425060","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":"Canonical force fields for interatomic interactions","authors":"Jack P. Schmittdiel ,&nbsp;Luis A. Rivera-Rivera ,&nbsp;Jay R. Walton","doi":"10.1016/j.chemphys.2025.112973","DOIUrl":"10.1016/j.chemphys.2025.112973","url":null,"abstract":"<div><div>Canonical approaches are applied to generate potentials and forces for interatomic interactions from <em>ab initio</em> data. The methodology has the advantage of generating highly accurate potentials and forces with a minimum number of <em>ab initio</em> points and without the need to fit or interpolate the data. In addition, forces are calculated directly from the <em>ab initio</em> points without the need to take the derivative of the potential. This is a significant advantage since there is no guarantee that the derivative of a function that represents the potential will represent the force curve accurately. The methodology is applied to the Ar-Ar and C₂H₆-Ar systems. Pair potentials and forces generated by canonical approaches are highly accurate and suitable for molecular dynamics simulations under extreme conditions of high temperature and pressure. In addition, canonical approaches accurately reproduce the attractive tail of interatomic potentials, which is very important in the field of ultracold chemistry.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112973"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425061","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 investigation of structural, elastic, electronic, optical and photocatalytic properties of Li2ZnSnO4","authors":"Konok Chandro Roy ,&nbsp;M. Riju Khandaker ,&nbsp;M.N.H. Liton ,&nbsp;M.M. Rahman ,&nbsp;M.S.I. Sarker ,&nbsp;M.K.R. Khan","doi":"10.1016/j.chemphys.2025.113028","DOIUrl":"10.1016/j.chemphys.2025.113028","url":null,"abstract":"<div><div>Li₂ZnSnO₄, belongs to the quaternary (I₂ − II − IV − O₄) type of semiconductors. It is an essential candidate for solar cells and optoelectronic applications. In this study, our goal is to investigate the structural, electrical, and optical properties of Li₂ZnSnO₄. These properties are calculated using density functional theory (DFT), based on the first principles computational methods. The optimized lattice constants are found to be <em>a</em> = 5.46, <em>b</em> = 11.41, and <em>c</em> = 8.61 Å, with angle β = 129.0^°. Li₂ZnSnO₄ compound demonstrates mechanical stability through its elastic tensor. It also exhibits soft, malleable, and highly machinable properties with poor elastic anisotropy. Two-dimensional and three-dimensional (2D and 3D) graphical visualizations are used to illustrate the elastic anisotropy. The material's stability is collectively ensured by its bond strength, Debye temperature, melting temperature, and Grüneisen parameter. Mülliken charge and bond analysis indicate a dominant ionic bonding character combined with covalent contributions. Li₂ZnSnO₄ exhibits a direct bandgap semiconductor with a bandgap energy of 2.01 eV. Various optical properties, such as dielectric response, absorption coefficient, reflectance, refractive index, photoconductivity, and energy loss characteristics have also been studied. The optical absorption coefficient is ∼10⁵ cm⁻¹ in the UV region. The low absorbance and reflectance of Li₂ZnSnO₄ compound in the infrared-to-visible region is a signature of transparent conducting oxide (TCO). Meeting redox potential conditions, Li₂ZnSnO₄ is considered as a promising photocatalyst for hydrogen generation and oxygen evolution.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113028"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576687","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":"Evaluation of neural network in multivariate interpolation of rate coefficients in air kinetics","authors":"I. Armenise ,&nbsp;F. Esposito ,&nbsp;G. Bonasia ,&nbsp;G. Micca Longo ,&nbsp;S. Longo","doi":"10.1016/j.chemphys.2025.113029","DOIUrl":"10.1016/j.chemphys.2025.113029","url":null,"abstract":"<div><div>The application of multilayer feedforward backpropagation neural network is investigated for the implementation of state-to-state rate coefficients in a chemically reacting air system, which includes excited vibrational states and radicals. An oxygen dissociation reaction is chosen as a case study because of its importance, and also to compare it with a high-end traditional fit in terms of various performances in isolation and within a kinetic model. Different network architectures are experimented and compared, by varying the number of layers and neurons. The indications provided are relevant for practical use of different data implementation techniques in complex kinetic models.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 113029"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576688","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":"Elucidating the activation mechanism of ESIPT dark state in Salicylidene Glycine Schiff bases via liquid–solid phase switching","authors":"Tianyu Cui,&nbsp;Siqi Wang,&nbsp;Xiaonan Wang,&nbsp;Yifu Zhang,&nbsp;Hui Li,&nbsp;Jixing Cai","doi":"10.1016/j.chemphys.2025.112981","DOIUrl":"10.1016/j.chemphys.2025.112981","url":null,"abstract":"<div><div>Understanding the effects of different environments and alkali metal substitution on the excited-state intramolecular proton transfer (ESIPT) process and emission mechanisms of luminescent materials is crucial for the design of next-generation solid-state emitters. In this study, the photophysical properties of three alkali-metal-substituted salicylidene diamine derivatives, GS-Li, GS-Na, and GS-K, were systematically investigated in methanol solution and in the solid, based on density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) approaches. In methanol, all three compounds exhibit barrierless ESIPT processes accompanied by twisted intramolecular charge transfer (TICT), resulting in fluorescence quenching. In the solid state, the crystal structure of GS-K exhibits characteristics resembling a hybrid of GS-Li and GS-Na. Therefore, our discussion focuses primarily on GS-Li and GS-Na, both of which display pronounced aggregation-induced emission (AIE) properties. GS-Li exhibits strong K* fluorescence emission through a barrierless ESIPT process coupled with an intramolecular charge transfer (ICT) mechanism. GS-Na undergoes barrierless ground-state intramolecular proton transfer (GSIPT) and exhibits K* fluorescence in the excited state. This work provides a comprehensive understanding of the ESIPT mechanisms and emission behaviors of these derivatives. It reveals the interplay among TICT, ICT, and ESIPT processes under different environments, offering valuable insights for the design and development of highly efficient luminescent materials with combined ESIPT and AIE characteristics.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112981"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474612","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}