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 phase of HfRhP as the most energetically stable, with an equilibrium lattice parameter of and a direct band gap of . 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 and figure of merit () 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.
{"title":"First-principles calculations to Investigate structural, Electronic, Optoelectronic, and Thermoelectric properties of HfRhP half-Heusler compound","authors":"M.K. Bamgbose , G.T. Solola , O.I. Atobatele , C.O. Ilabija , J.M. Whetode , 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}
Pub Date : 2026-03-01Epub Date: 2025-11-15DOI: 10.1016/j.chemphys.2025.113022
Evren Görkem Özdemir , Wisam Ayad Ahmed Ahmed
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 μB/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.
{"title":"Comprehensive analysis of half-metallic, mechanical, electronic, thermodynamic, and optical properties of single perovskites LiCrZ3 (Z = Cl, Br, I)","authors":"Evren Görkem Özdemir , 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 LiCrZ<sub>3</sub> (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<sub>B</sub>/f.u. for LiCrZ<sub>3</sub>. The most partial contributions in each group came from Cr-transition metals. LiCrZ<sub>3</sub> 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 LiCrCl<sub>3</sub>. While the remarkable electronic, magnetic, elastic, and thermodynamic properties of LiCrZ<sub>3</sub> (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}
Pub Date : 2026-03-01Epub Date: 2025-10-17DOI: 10.1016/j.chemphys.2025.112976
Murillo H. Queiroz , Tiago V. Alves , Roberto Rivelino
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.
{"title":"Cooperative and stabilization effects in hydrogen-bonded chains of microhydrated thymine: a QTAIM and TD-DFT study","authors":"Murillo H. Queiroz , Tiago V. Alves , 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}
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.
{"title":"Understanding the structures and dynamics of protic [EtNH3][NO3] and aprotic [Emim][NTF₂] ionic liquid mixtures from molecular dynamics simulation","authors":"Wenshu Liang, Dong Wang, Jia-ni Fan, Guangli Zhou, Qiying Xia, Xia Leng, 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 [EtNH<sub>3</sub>][NO<sub>3</sub>] and aprotic [Emim][NTF<sub>2</sub>] ionic liquid mixtures forming {[Emim][NTF<sub>2</sub>]}<sub>x</sub>{[EtNH<sub>3</sub>][NO<sub>3</sub>]}<sub>(1-x)</sub> 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 cm<sup>3</sup>·mol<sup>−1</sup>. Further analysis indicates that the translational as well as rotational motions of [Emim]<sup>+</sup> and [NTF<sub>2</sub>]<sup>−</sup> are restricted significantly with the decreasing the molar fractions. However, for [EtNH<sub>3</sub>]<sup>+</sup> and [NO<sub>3</sub>]<sup>−</sup>, they display similar restrictions with the increasing the molar fractions in IL mixtures. Such restrictions can be attributed to the enhanced HB dynamics between [EtNH<sub>3</sub>]<sup>+</sup> and [NO<sub>3</sub>]<sup>−</sup> in the IL mixtures. Moreover, the HB strength of [Emim]<sup>+</sup>-[NTF<sub>2</sub>]<sup>−</sup> is enhanced with decreasing molar fractions in the IL mixtures, which can be better explained by the slower translational and rotational motions for [Emim]<sup>+</sup> and [NTF₂]<sup>−</sup> 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 [EtNH<sub>3</sub>][NO<sub>3</sub>] and aprotic [Emim][NTF<sub>2</sub>] 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}
Pub Date : 2026-03-01Epub Date: 2025-10-25DOI: 10.1016/j.chemphys.2025.112979
Hongsheng Zhao , Yuhao Chen , Bingyin Feng , Xubiao Wang , Xiliang Zhang , Qian Yang , Jing Zhao , Yinfeng Li , Yanhui Wang
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.
{"title":"First-principles study of ga-doped γ-TiAl intermetallic compound","authors":"Hongsheng Zhao , Yuhao Chen , Bingyin Feng , Xubiao Wang , Xiliang Zhang , Qian Yang , Jing Zhao , Yinfeng Li , 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}
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.
{"title":"Field-free orientation of LiH molecules controlled by a train of few-cycle/single-cycle terahertz laser pulses","authors":"Yuemin Leng, Wenqian Li, Yaoyao Wei, Shou Chai, Gaoren Wang, Yongchang Han, 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}
Pub Date : 2026-03-01Epub Date: 2025-10-21DOI: 10.1016/j.chemphys.2025.112973
Jack P. Schmittdiel , Luis A. Rivera-Rivera , Jay R. Walton
Canonical approaches are applied to generate potentials and forces for interatomic interactions from ab initio data. The methodology has the advantage of generating highly accurate potentials and forces with a minimum number of ab initio points and without the need to fit or interpolate the data. In addition, forces are calculated directly from the ab initio 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.
{"title":"Canonical force fields for interatomic interactions","authors":"Jack P. Schmittdiel , Luis A. Rivera-Rivera , 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 C<sub>2</sub>H<sub>6</sub>-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}
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.
{"title":"Elucidating the activation mechanism of ESIPT dark state in Salicylidene Glycine Schiff bases via liquid–solid phase switching","authors":"Tianyu Cui, Siqi Wang, Xiaonan Wang, Yifu Zhang, Hui Li, 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}
Pub Date : 2026-03-01Epub Date: 2025-11-04DOI: 10.1016/j.chemphys.2025.112966
Fengqin Cao , Huan Wen , Huaxin Zhang , Xiaohong Yang , Huihui He , Wei Hu
Li-rich layered oxides are a promising cathode material for next-generation Li-ion batteries due to their high energy density. However, the evolution of oxygen during cycling limits their application. Currently, numerous failure mechanisms remain poorly understood by the scientific community for Li-rich cathodes. Herein, the role of Li-ion in the transition metal layer was systematically studied by employing the first-principles calculation method. The findings show that Li-ion in the transition metal layer is beneficial to enhancing the intercalation potential, improving the electronic conductivity, increasing the theoretical capacity and reducing the Jahn-Teller distortion for Li-rich cathode. It also has an inhibitory effect on the volume change of the cathode at low Li content. However, the increase of Li content will increase the instability of lattice oxygen for Li-rich cathode. This work clarifies the role of Li-ion in the transition metal layer, which is conducive to the design of high-performance Li-rich cathode materials.
{"title":"Role of Li-ion in transition metal layer for Li-rich cathode: insights from first-principles calculations","authors":"Fengqin Cao , Huan Wen , Huaxin Zhang , Xiaohong Yang , Huihui He , Wei Hu","doi":"10.1016/j.chemphys.2025.112966","DOIUrl":"10.1016/j.chemphys.2025.112966","url":null,"abstract":"<div><div>Li-rich layered oxides are a promising cathode material for next-generation Li-ion batteries due to their high energy density. However, the evolution of oxygen during cycling limits their application. Currently, numerous failure mechanisms remain poorly understood by the scientific community for Li-rich cathodes. Herein, the role of Li-ion in the transition metal layer was systematically studied by employing the first-principles calculation method. The findings show that Li-ion in the transition metal layer is beneficial to enhancing the intercalation potential, improving the electronic conductivity, increasing the theoretical capacity and reducing the Jahn-Teller distortion for Li-rich cathode. It also has an inhibitory effect on the volume change of the cathode at low Li content. However, the increase of Li content will increase the instability of lattice oxygen for Li-rich cathode. This work clarifies the role of Li-ion in the transition metal layer, which is conducive to the design of high-performance Li-rich cathode materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"602 ","pages":"Article 112966"},"PeriodicalIF":2.4,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474916","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}
Pub Date : 2026-03-01Epub Date: 2025-11-14DOI: 10.1016/j.chemphys.2025.113028
Konok Chandro Roy , M. Riju Khandaker , M.N.H. Liton , M.M. Rahman , M.S.I. Sarker , M.K.R. Khan
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 a = 5.46, b = 11.41, and c = 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.
Li2ZnSnO4，属于四元（I2−II−IV−O4）型半导体。它是太阳能电池和光电子应用的重要候选材料。在这项研究中，我们的目标是研究Li2ZnSnO4的结构、电学和光学性质。这些性质是利用密度泛函理论（DFT）计算的，基于第一性原理计算方法。优化后的晶格常数为a = 5.46, b = 11.41, c = 8.61 Å，角β = 129.0°。Li2ZnSnO4化合物通过弹性张量表现出力学稳定性。它还表现出柔软，延展性和高度可加工性能，弹性各向异性差。采用二维和三维（二维和三维）图形可视化来说明弹性各向异性。材料的稳定性由其结合强度、德拜温度、熔化温度和格力尼森参数共同保证。m lliken电荷和键分析表明，主要的离子键特征结合共价贡献。Li2ZnSnO4表现为直接带隙半导体，带隙能量为2.01 eV。各种光学性质，如介电响应、吸收系数、反射率、折射率、光电导率和能量损失特性也进行了研究。在紫外区光学吸收系数为~ 105 cm−1。Li2ZnSnO4化合物在红外-可见光区具有较低的吸光度和反射率，是透明导电氧化物（TCO）的特征。在满足氧化还原电位条件下，Li2ZnSnO4被认为是一种很有前途的产氢析氧光催化剂。
{"title":"First-principles investigation of structural, elastic, electronic, optical and photocatalytic properties of Li2ZnSnO4","authors":"Konok Chandro Roy , M. Riju Khandaker , M.N.H. Liton , M.M. Rahman , M.S.I. Sarker , M.K.R. Khan","doi":"10.1016/j.chemphys.2025.113028","DOIUrl":"10.1016/j.chemphys.2025.113028","url":null,"abstract":"<div><div>Li<sub>2</sub>ZnSnO<sub>4</sub>, belongs to the quaternary (I<sub>2</sub> − II − IV − O<sub>4</sub>) 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 Li<sub>2</sub>ZnSnO<sub>4</sub>. 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<sup>°</sup>. Li<sub>2</sub>ZnSnO<sub>4</sub> 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. Li<sub>2</sub>ZnSnO<sub>4</sub> 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 ∼10<sup>5</sup> cm<sup>−1</sup> in the UV region. The low absorbance and reflectance of Li<sub>2</sub>ZnSnO<sub>4</sub> compound in the infrared-to-visible region is a signature of transparent conducting oxide (TCO). Meeting redox potential conditions, Li<sub>2</sub>ZnSnO<sub>4</sub> 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}
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