Pub Date : 2025-12-29DOI: 10.1016/j.comptc.2025.115651
Jumei Zhang , Ziheng Zhang , Menghan Zhao , Weiwei Chen , Jiao Wang , Jinghan Zou , Xiangtao Kong , Hua Xie , Hongjin Qiao
Carbon monoxide (CO) oxidation is pivotal for exhaust-gas purification. Ambient co-adsorbates nitrogen monoxide (NO) can significantly affect CO oxidation. Herein, a series of NbNiO(NO)(CO)n− (n = 1–6) clusters were investigated by density functional theory. A bridging-O structure is most favorable for n = 1–3, then a terminal-O structure becomes favored for n = 4–5, and finally a CO2-tagged structure is most favorable for n = 6. NO preferentially adsorbs at niobium (Nb) site, promoting CO oxidation by mediating the NbO interactions. During the consecutive CO adsorption, NO acts as an electron donor, and the metal centers display complementary electron transfer behavior: Nb acts as an electron acceptor for n ≤ 3, then switches to an electron donor at n = 4–5, and finally acts as an electron acceptor at n = 6, whereas nickel (Ni) exhibits the opposite trend. These findings provide atomistic insights into CO oxidation over heteronuclear metal oxides under co-adsorption conditions.
{"title":"CO oxidation on noble-metal-free niobium‑nickel monoxide anion under NO/CO Co-adsorption","authors":"Jumei Zhang , Ziheng Zhang , Menghan Zhao , Weiwei Chen , Jiao Wang , Jinghan Zou , Xiangtao Kong , Hua Xie , Hongjin Qiao","doi":"10.1016/j.comptc.2025.115651","DOIUrl":"10.1016/j.comptc.2025.115651","url":null,"abstract":"<div><div>Carbon monoxide (CO) oxidation is pivotal for exhaust-gas purification. Ambient co-adsorbates nitrogen monoxide (NO) can significantly affect CO oxidation. Herein, a series of NbNiO(NO)(CO)<sub><em>n</em></sub><sup>−</sup> (<em>n</em> = 1–6) clusters were investigated by density functional theory. A bridging-O structure is most favorable for <em>n</em> = 1–3, then a terminal-O structure becomes favored for <em>n</em> = 4–5, and finally a CO<sub>2</sub>-tagged structure is most favorable for <em>n</em> = 6. NO preferentially adsorbs at niobium (Nb) site, promoting CO oxidation by mediating the Nb<img>O interactions. During the consecutive CO adsorption, NO acts as an electron donor, and the metal centers display complementary electron transfer behavior: Nb acts as an electron acceptor for <em>n</em> ≤ 3, then switches to an electron donor at <em>n</em> = 4–5, and finally acts as an electron acceptor at <em>n</em> = 6, whereas nickel (Ni) exhibits the opposite trend. These findings provide atomistic insights into CO oxidation over heteronuclear metal oxides under co-adsorption conditions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115651"},"PeriodicalIF":3.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880313","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 : 2025-12-29DOI: 10.1016/j.comptc.2025.115647
Huan Yuan , Kaidong Shen , Chang Xu , Qiquan Luo
Calcium-ion batteries (CIBs) represent a promising next-generation energy storage technology due to earth-abundant of calcium element and high theoretical energy density. However, the application of CIBs is still hindered by the lack of high-performance anode materials, particularly those suffering from limited storage capacity and sluggish diffusion kinetics induced by large ionic radius of Ca ion. To address this challenge, this paper proposes a porous superatom-assembled B₄C₄ monolayer from first principles calculation, as a promising anode candidate for CIBs. Electronic analysis confirms the 14e superatomic shell of B₄C2 building block, which linked by two edge carbon atoms with unpaired electrons resulting in an antiferromagnetic ground state. This electronic configuration significantly enhances the material's affinity for Ca, due to the formation of multi-center bonding between Ca and single-occupied C atoms. Remarkably, the B₄C₄ anode delivers an ultrahigh theoretical capacity of 3495.80 mAh g−1, with a low Ca ion diffusion barrier of 0.59 eV, facilitating rapid charge/discharge rates. The average open-circuit voltage is decrease gradually from 0.94 V to 0.20 V with increasing Ca concentration. This work not only predicts a promising anode candidate for CIBs, but also establishes antiferromagnetic materials with unpair electron as a new paradigm for advanced battery design.
钙离子电池具有丰富的钙元素和较高的理论能量密度，是一种很有前途的下一代储能技术。然而，高性能阳极材料的缺乏仍然阻碍了cib的应用，特别是由于Ca离子的大离子半径导致的存储容量有限和扩散动力学缓慢。为了解决这一挑战，本文从第一性原理计算中提出了一种多孔超原子组装的B₄C₄单层，作为cib的有希望的阳极候选材料。电子分析证实了B₄C2构建块的14e超原子壳层，它由两个边缘碳原子与不成对电子连接，导致反铁磁基态。由于Ca和单占据的C原子之间形成了多中心键，这种电子构型显著增强了材料对Ca的亲和力。值得注意的是，B₄C₄阳极提供了3495.80 mAh g−1的超高理论容量，具有0.59 eV的低Ca离子扩散势垒，有利于快速充放电。随着Ca浓度的增加，平均开路电压从0.94 V逐渐降低到0.20 V。这项工作不仅预测了一种有希望的cib阳极候选材料，而且为先进电池设计建立了一种具有解对电子的反铁磁性材料。
{"title":"Antiferromagnetic B₄C₄ superatomic monolayer acting as high-capacity calcium-ion battery anode","authors":"Huan Yuan , Kaidong Shen , Chang Xu , Qiquan Luo","doi":"10.1016/j.comptc.2025.115647","DOIUrl":"10.1016/j.comptc.2025.115647","url":null,"abstract":"<div><div>Calcium-ion batteries (CIBs) represent a promising next-generation energy storage technology due to earth-abundant of calcium element and high theoretical energy density. However, the application of CIBs is still hindered by the lack of high-performance anode materials, particularly those suffering from limited storage capacity and sluggish diffusion kinetics induced by large ionic radius of Ca ion. To address this challenge, this paper proposes a porous superatom-assembled B₄C₄ monolayer from first principles calculation, as a promising anode candidate for CIBs. Electronic analysis confirms the 14e superatomic shell of B₄C<sub>2</sub> building block, which linked by two edge carbon atoms with unpaired electrons resulting in an antiferromagnetic ground state. This electronic configuration significantly enhances the material's affinity for Ca, due to the formation of multi-center bonding between Ca and single-occupied C atoms. Remarkably, the B₄C₄ anode delivers an ultrahigh theoretical capacity of 3495.80 mAh g<sup>−1</sup>, with a low Ca ion diffusion barrier of 0.59 eV, facilitating rapid charge/discharge rates. The average open-circuit voltage is decrease gradually from 0.94 V to 0.20 V with increasing Ca concentration. This work not only predicts a promising anode candidate for CIBs, but also establishes antiferromagnetic materials with unpair electron as a new paradigm for advanced battery design.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115647"},"PeriodicalIF":3.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880325","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 : 2025-12-29DOI: 10.1016/j.comptc.2025.115653
S. Bendouda, M. Batouche, M.E.A. El Goutni, T. Seddik, Baltach Hadj
This comprehensive study employs density functional theory (DFT) calculations within the WIEN2k framework to systematically explore the structural, electronic, optical, and photocatalytic properties of phosphorus-rich Zintl-phase compounds X₄P₆, where X represents the alkali metals K, Rb, or Cs. Electronic structure calculations using the HSE hybrid functional reveal indirect bandgaps ranging from 1.23 eV (K₄P₆) to 1.40 eV (Cs₄P₆), optimally positioned for visible-light absorption, with enhanced charge-carrier dynamics driven by orbital hybridization. Optical characterizations demonstrate strong absorption coefficients exceeding 20 × 104 cm−1 across the visible spectrum, with K₄P₆ exhibiting superior light-harvesting efficiency. Band-edge alignment calculations confirm thermodynamic suitability for spontaneous water splitting, with conduction-band minima at −0.11 to −0.20 eV and valence-band maxima at +1.12 to +1.20 eV versus the normal hydrogen electrode (NHE), with Cs₄P₆ offering optimal overpotentials. This extended analysis, enriched with in-depth physical insights into lattice dynamics, charge transport, and optical interactions, establishes X₄P₆ compounds as highly promising candidates for sustainable solar-to‑hydrogen energy conversion, with potential for further optimization through compositional engineering.
这项综合研究采用WIEN2k框架内的密度泛函理论（DFT）计算，系统地探索了富磷锌相化合物X₄P₆的结构、电子、光学和光催化性能，其中X代表碱金属K、Rb或Cs。利用HSE杂化泛函进行的电子结构计算显示，间接带隙范围从1.23 eV （K₄P₆）到1.40 eV （Cs₄P₆），最适合可见光吸收，轨道杂化驱动的电荷载流子动力学增强。光学表征表明，在可见光谱上，K₄P₆的吸收系数超过20 × 104 cm−1，具有优异的光捕获效率。带边校准计算证实了自发水分解的热力学适用性，与普通氢电极（NHE）相比，导带最小值为- 0.11至- 0.20 eV，价带最大值为+1.12至+1.20 eV， Cs₄P₆提供最佳过电位。这一扩展分析，丰富了对晶格动力学、电荷输运和光相互作用的深入物理见解，确立了X₄P₆化合物作为可持续太阳能到氢能源转换的极有前途的候选者，并有可能通过成分工程进一步优化。
{"title":"First-principles investigation of phosphorus-rich Zintl phases X₄P₆ (X = K, Rb, Cs) for efficient visible-light-driven photocatalytic energy conversion","authors":"S. Bendouda, M. Batouche, M.E.A. El Goutni, T. Seddik, Baltach Hadj","doi":"10.1016/j.comptc.2025.115653","DOIUrl":"10.1016/j.comptc.2025.115653","url":null,"abstract":"<div><div>This comprehensive study employs density functional theory (DFT) calculations within the WIEN2k framework to systematically explore the structural, electronic, optical, and photocatalytic properties of phosphorus-rich Zintl-phase compounds X₄P₆, where X represents the alkali metals K, Rb, or Cs. Electronic structure calculations using the HSE hybrid functional reveal indirect bandgaps ranging from 1.23 eV (K₄P₆) to 1.40 eV (Cs₄P₆), optimally positioned for visible-light absorption, with enhanced charge-carrier dynamics driven by orbital hybridization. Optical characterizations demonstrate strong absorption coefficients exceeding 20 × 10<sup>4</sup> cm<sup>−1</sup> across the visible spectrum, with K₄P₆ exhibiting superior light-harvesting efficiency. Band-edge alignment calculations confirm thermodynamic suitability for spontaneous water splitting, with conduction-band minima at −0.11 to −0.20 eV and valence-band maxima at +1.12 to +1.20 eV versus the normal hydrogen electrode (NHE), with Cs₄P₆ offering optimal overpotentials. This extended analysis, enriched with in-depth physical insights into lattice dynamics, charge transport, and optical interactions, establishes X₄P₆ compounds as highly promising candidates for sustainable solar-to‑hydrogen energy conversion, with potential for further optimization through compositional engineering.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115653"},"PeriodicalIF":3.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880312","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 adsorption behaviour of five phosphorus-bearing molecules (PO, PO2, POH, HPO and PH3) on amorphous silica, as a representative model not only for interstellar silicate dust grains but also for terrestrial silicate surfaces that play a role in prebiotic and geochemical processes, has been investigated to elucidate their sorption and spectroscopic characteristics. The dispersion-corrected density functional theory (DFT-D3) within the VASP framework was employed. The calculated adsorption energies are all negative, indicating that the adsorption processes are exothermic and thermodynamically favorable. Intermolecular distances and Bader charges confirm chemisorption as the dominant interaction mode, consistent with the observed energetics. Infrared (IR) spectra further demonstrate the formation of chemical bonds between the adsorbed species and the silica surface. While the spectra of PO and PO₂ exhibit similarities and overlapping vibrational features, the PO₂ spectrum can be uniquely identified by an asymmetric stretching vibration at 1253 cm−1. The POH spectrum is distinguished by a peak at 2301 cm−1, arising from the interaction of phosphorus with a silanol hydrogen. The HPO spectrum features a characteristic peak at 2075 cm−1, corresponding to the H–PO stretching vibration. Finally, PH3 exhibits peaks at 2313 cm−1, assigned to the PH stretching vibration.
{"title":"Computational study of phosphorus-bearing molecule adsorption on amorphous silica: energetics and infrared signatures with relevance for interstellar and terrestrial chemistry","authors":"Mireille Amandjigbeto , Etienne P. Hessou , Gaston Kpotin , Yacolé G.S. Atohoun , Ionut Tranca , Vicente Timon , Frederik Tielens","doi":"10.1016/j.comptc.2025.115652","DOIUrl":"10.1016/j.comptc.2025.115652","url":null,"abstract":"<div><div>The adsorption behaviour of five phosphorus-bearing molecules (PO, PO<sub>2</sub>, POH, HPO and PH<sub>3</sub>) on amorphous silica, as a representative model not only for interstellar silicate dust grains but also for terrestrial silicate surfaces that play a role in prebiotic and geochemical processes, has been investigated to elucidate their sorption and spectroscopic characteristics. The dispersion-corrected density functional theory (DFT-D3) within the VASP framework was employed. The calculated adsorption energies are all negative, indicating that the adsorption processes are exothermic and thermodynamically favorable. Intermolecular distances and Bader charges confirm chemisorption as the dominant interaction mode, consistent with the observed energetics. Infrared (IR) spectra further demonstrate the formation of chemical bonds between the adsorbed species and the silica surface. While the spectra of PO and PO₂ exhibit similarities and overlapping vibrational features, the PO₂ spectrum can be uniquely identified by an asymmetric stretching vibration at 1253 cm<sup>−1</sup>. The POH spectrum is distinguished by a peak at 2301 cm<sup>−1</sup>, arising from the interaction of phosphorus with a silanol hydrogen. The HPO spectrum features a characteristic peak at 2075 cm<sup>−1</sup>, corresponding to the H–PO stretching vibration. Finally, PH<sub>3</sub> exhibits peaks at 2313 cm<sup>−1</sup>, assigned to the P<img>H stretching vibration.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115652"},"PeriodicalIF":3.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923699","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 : 2025-12-27DOI: 10.1016/j.comptc.2025.115649
Qamar Abuhassan , G. PadmaPriya , Subhashree Ray , Amrita Pal , Vimal Arora , Ahmed Aldulaimi , Omayma Salim Waleed , Rafid Jihad Albadr , Aseel Smerat , Akmal Abilkasimov , Kamoliddin Ziyaev
Atomistic insights into the impact of elemental doping are crucial for the rational design of high-performance gas sensors based on two-dimensional carbon materials. In this work, we theoretically investigate the influence of nitrogen (N) and phosphorus (P) doping on the sensing properties of T-graphene toward sulfur trioxide (SO₃) using density functional theory at the M062X/6-31 g(d,p) level. Doping significantly alters the monolayer's structural, electronic, and vibrational properties, inducing charge separation. This is evidenced by an increase in the dipole moment from zero in pristine T-graphene to 2.19 Debye and 2.16 Debye for the N- and P-doped systems, respectively. For SO₃ adsorption, interaction with pristine T-graphene is weak physisorption, characterized by a low adsorption energy of −8.82 kcal/mol and negligible charge transfer. Doping substantially enhances reactivity: adsorption energies increase to −10.23 kcal/mol and − 18.49 kcal/mol for the N- and P-doped systems, respectively. This enhancement correlates with a significant change in the energy gap of 9.40 % for N-doping and 27.11 % for P-doping, indicating high sensitivity. Natural Bond Orbital (NBO) analysis further confirms that both doped systems act as charge donors, with calculated charge transfers of 0.13 e and 0.49 e for N- and P-doped T-graphene, respectively.”
{"title":"Unveiling the mechanism of enhanced SO₃ sensing on P-doped T-graphene: The critical roles of donor-acceptor interactions and dopant hybridization","authors":"Qamar Abuhassan , G. PadmaPriya , Subhashree Ray , Amrita Pal , Vimal Arora , Ahmed Aldulaimi , Omayma Salim Waleed , Rafid Jihad Albadr , Aseel Smerat , Akmal Abilkasimov , Kamoliddin Ziyaev","doi":"10.1016/j.comptc.2025.115649","DOIUrl":"10.1016/j.comptc.2025.115649","url":null,"abstract":"<div><div>Atomistic insights into the impact of elemental doping are crucial for the rational design of high-performance gas sensors based on two-dimensional carbon materials. In this work, we theoretically investigate the influence of nitrogen (N) and phosphorus (P) doping on the sensing properties of T-graphene toward sulfur trioxide (SO₃) using density functional theory at the M062X/6-31 g(d,p) level. Doping significantly alters the monolayer's structural, electronic, and vibrational properties, inducing charge separation. This is evidenced by an increase in the dipole moment from zero in pristine T-graphene to 2.19 Debye and 2.16 Debye for the N- and P-doped systems, respectively. For SO₃ adsorption, interaction with pristine T-graphene is weak physisorption, characterized by a low adsorption energy of −8.82 kcal/mol and negligible charge transfer. Doping substantially enhances reactivity: adsorption energies increase to −10.23 kcal/mol and − 18.49 kcal/mol for the N- and P-doped systems, respectively. This enhancement correlates with a significant change in the energy gap of 9.40 % for N-doping and 27.11 % for P-doping, indicating high sensitivity. Natural Bond Orbital (NBO) analysis further confirms that both doped systems act as charge donors, with calculated charge transfers of 0.13 e and 0.49 e for N- and P-doped T-graphene, respectively.”</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115649"},"PeriodicalIF":3.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880326","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 : 2025-12-26DOI: 10.1016/j.comptc.2025.115645
Xiurong Yang , Jia Dang , Chi Zhang , Bo Liu , Haixia Ma
Metal oxides are widely used as combustion catalysts in propellants to promote the decomposition of energetic materials (EMs). To elucidate the underlying catalytic mechanism and facilitate the screening of effective catalysts, we employed density functional theory (DFT) to study the interactions of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and its key decomposition product NO2 with various metal oxides. The adsorption behavior was correlated with the thermal decomposition performance of RDX/metal oxide mixtures. While only slight bond stretching in RDX was observed upon adsorption, strong adsorption of NO2 was found to correlate with enhanced decomposition rates and lower activation energy for RDX. This trend was further validated in RDX/composite metal oxides systems. Our findings suggest that NO2 adsorption energy can serve as an efficient and practical factor for predicting the catalytic activity of metal oxides toward RDX decomposition.
{"title":"Revealing the crucial role of dissociated product NO2 in RDX catalyzed by metal oxides: A combined DFT and experimental study","authors":"Xiurong Yang , Jia Dang , Chi Zhang , Bo Liu , Haixia Ma","doi":"10.1016/j.comptc.2025.115645","DOIUrl":"10.1016/j.comptc.2025.115645","url":null,"abstract":"<div><div>Metal oxides are widely used as combustion catalysts in propellants to promote the decomposition of energetic materials (EMs). To elucidate the underlying catalytic mechanism and facilitate the screening of effective catalysts, we employed density functional theory (DFT) to study the interactions of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and its key decomposition product NO<sub>2</sub> with various metal oxides. The adsorption behavior was correlated with the thermal decomposition performance of RDX/metal oxide mixtures. While only slight bond stretching in RDX was observed upon adsorption, strong adsorption of NO<sub>2</sub> was found to correlate with enhanced decomposition rates and lower activation energy for RDX. This trend was further validated in RDX/composite metal oxides systems. Our findings suggest that NO<sub>2</sub> adsorption energy can serve as an efficient and practical factor for predicting the catalytic activity of metal oxides toward RDX decomposition.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115645"},"PeriodicalIF":3.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880311","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 : 2025-12-26DOI: 10.1016/j.comptc.2025.115646
Bhushan Dharmadhikari , Peiqiao Wu , Prabir Patra
Understanding the molecular interactions between proteins and carbon nanotubes (CNTs) is critical for optimizing the function and stability of protein-CNT interfaces. In this work, we use all-atom molecular dynamics simulations to examine how SP-B and SP-C adsorb onto an armchair (6,6) single-walled carbon nanotube (SWCNT) and how interfacial water influences this process. The two proteins follow distinct adsorption pathways: SP-B reaches stable contact with the nanotube within ∼2.5 ns, whereas SP-C requires ∼15 ns. Residue-level analysis shows that SP-B engages the surface through localized interactions, including π–π stacking involving its N-terminal phenylalanine (PHE-SWCNT), whereas SP-C forms more extended hydrophobic contacts along its longer α-helix, including CH–π interactions involving aliphatic and proline side chains with the SWCNT surface. The hydration environment also differs significantly. SP-B maintains a relatively stable hydration shell and forms more frequent protein-water hydrogen bonds, whereas SP-C exhibits intermittent “dry” interfacial states as it spreads over the nanotube. These dehydration events correlate with a secondary stabilization in its van der Waals interaction energy later in the trajectory. Taken together, the results show that the intrinsic structural features of SP-B and SP-C give rise to different adsorption dynamics and interfacial hydration responses. These findings help clarify how the molecular environment governs protein behavior at the nanoscale, informing the development of more effective protein-CNT biosensors.
{"title":"Interactions between carbon nanotubes and pulmonary surfactant proteins: the role of interfacial water molecules","authors":"Bhushan Dharmadhikari , Peiqiao Wu , Prabir Patra","doi":"10.1016/j.comptc.2025.115646","DOIUrl":"10.1016/j.comptc.2025.115646","url":null,"abstract":"<div><div>Understanding the molecular interactions between proteins and carbon nanotubes (CNTs) is critical for optimizing the function and stability of protein-CNT interfaces. In this work, we use all-atom molecular dynamics simulations to examine how SP-B and SP-C adsorb onto an armchair (6,6) single-walled carbon nanotube (SWCNT) and how interfacial water influences this process. The two proteins follow distinct adsorption pathways: SP-B reaches stable contact with the nanotube within ∼2.5 ns, whereas SP-C requires ∼15 ns. Residue-level analysis shows that SP-B engages the surface through localized interactions, including π–π stacking involving its N-terminal phenylalanine (PHE-SWCNT), whereas SP-C forms more extended hydrophobic contacts along its longer α-helix, including CH–π interactions involving aliphatic and proline side chains with the SWCNT surface. The hydration environment also differs significantly. SP-B maintains a relatively stable hydration shell and forms more frequent protein-water hydrogen bonds, whereas SP-C exhibits intermittent “dry” interfacial states as it spreads over the nanotube. These dehydration events correlate with a secondary stabilization in its van der Waals interaction energy later in the trajectory. Taken together, the results show that the intrinsic structural features of SP-B and SP-C give rise to different adsorption dynamics and interfacial hydration responses. These findings help clarify how the molecular environment governs protein behavior at the nanoscale, informing the development of more effective protein-CNT biosensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115646"},"PeriodicalIF":3.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880314","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 : 2025-12-24DOI: 10.1016/j.comptc.2025.115644
Tamer S. EL-Shazly , Morad M. El-Hendawy
First-principles calculations using the revised Perdew–Burke–Ernzerhof (PBEsol) functional were performed to investigate the effects of noble-metal intercalation (Pt, Au, and Ag) on the electronic and optical properties of B-Nb₂O₅. Band structure analysis reveals that pristine B-Nb₂O₅ is an indirect bandgap semiconductor with a gap of 2.66 eV. Remarkably, intercalation substantially narrows the bandgap, yielding direct bandgap materials — B-Nb₂O₅:Au (0.94 eV) and B-Nb₂O₅: Ag (0.28 eV) — and an indirect bandgap material, B-Nb₂O₅:Pt (1.89 eV). This bandgap reduction primarily arises from a downward shift in the conduction band. Estimated charge carrier concentrations, derived using a Boltzmann-like distribution, indicate promising values for solar energy conversion. Furthermore, the absorption spectra exhibit a pronounced redshift across the 300–1000 nm range upon intercalation. Analysis of the dielectric function and refractive index further reveals enhanced electronic contributions to the dielectric constant and notable cladding characteristics. These findings suggest that noble-metal-intercalated B-Nb₂O₅ systems are promising candidates for solar energy conversion and optical device applications.
{"title":"Noble-metal intercalation effects on the electronic and optical properties of B-Nb₂O₅","authors":"Tamer S. EL-Shazly , Morad M. El-Hendawy","doi":"10.1016/j.comptc.2025.115644","DOIUrl":"10.1016/j.comptc.2025.115644","url":null,"abstract":"<div><div>First-principles calculations using the revised Perdew–Burke–Ernzerhof (PBEsol) functional were performed to investigate the effects of noble-metal intercalation (Pt, Au, and Ag) on the electronic and optical properties of B-Nb₂O₅. Band structure analysis reveals that pristine B-Nb₂O₅ is an indirect bandgap semiconductor with a gap of 2.66 eV. Remarkably, intercalation substantially narrows the bandgap, yielding direct bandgap materials — B-Nb₂O₅:Au (0.94 eV) and B-Nb₂O₅: Ag (0.28 eV) — and an indirect bandgap material, B-Nb₂O₅:Pt (1.89 eV). This bandgap reduction primarily arises from a downward shift in the conduction band. Estimated charge carrier concentrations, derived using a Boltzmann-like distribution, indicate promising values for solar energy conversion. Furthermore, the absorption spectra exhibit a pronounced redshift across the 300–1000 nm range upon intercalation. Analysis of the dielectric function and refractive index further reveals enhanced electronic contributions to the dielectric constant and notable cladding characteristics. These findings suggest that noble-metal-intercalated B-Nb₂O₅ systems are promising candidates for solar energy conversion and optical device applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115644"},"PeriodicalIF":3.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836692","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 : 2025-12-21DOI: 10.1016/j.comptc.2025.115642
Ying Duan , Jide Zhang , Shuai Yuan , YunPeng Ge , ZengMing Qin , ShuaiWei Wang
The adsorption of three typical dissolved gases (CO, C2H2, and C2H4) from oil-immersed transformers on Pd-modified g-C3N4 was studied by DFT. A strong interaction is observed between the Pd atom and the C3N4, indicated by a binding energy of −4.936 eV. To understand the adsorption characteristics of the Pd-C3N4, we fully analyzed its adsorption configurations, charge density difference, and electronic properties. This analysis results that chemisorption occurs in three systems. The sensing response was analyzed to evaluate the resistive sensing potential of the Pd-C3N4 for CO, C2H2, and C2H4. The results indicate a high sensitivity for these gases. WF analysis reveals the potential of the Pd-C3N4 for WF-based C2H4 sensing. The results indicate that the Pd-C3N4 holds significant promise for dissolved gas sensing. This suggests it could be further explored as a typical sensing device to monitor the operational status of oil-immersed transformers, providing a valuable tool for condition assessment.
{"title":"Highly sensitive detection of dissolved transformer gases on Pd modified g-C3N4:A first-principles study","authors":"Ying Duan , Jide Zhang , Shuai Yuan , YunPeng Ge , ZengMing Qin , ShuaiWei Wang","doi":"10.1016/j.comptc.2025.115642","DOIUrl":"10.1016/j.comptc.2025.115642","url":null,"abstract":"<div><div>The adsorption of three typical dissolved gases (CO, C<sub>2</sub>H<sub>2</sub>, and C<sub>2</sub>H<sub>4</sub>) from oil-immersed transformers on Pd-modified g-C<sub>3</sub>N<sub>4</sub> was studied by DFT. A strong interaction is observed between the Pd atom and the C<sub>3</sub>N<sub>4</sub>, indicated by a binding energy of −4.936 eV. To understand the adsorption characteristics of the Pd-C<sub>3</sub>N<sub>4</sub>, we fully analyzed its adsorption configurations, charge density difference, and electronic properties. This analysis results that chemisorption occurs in three systems. The sensing response was analyzed to evaluate the resistive sensing potential of the Pd-C<sub>3</sub>N<sub>4</sub> for CO, C<sub>2</sub>H<sub>2</sub>, and C<sub>2</sub>H<sub>4</sub>. The results indicate a high sensitivity for these gases. WF analysis reveals the potential of the Pd-C<sub>3</sub>N<sub>4</sub> for WF-based C<sub>2</sub>H<sub>4</sub> sensing. The results indicate that the Pd-C<sub>3</sub>N<sub>4</sub> holds significant promise for dissolved gas sensing. This suggests it could be further explored as a typical sensing device to monitor the operational status of oil-immersed transformers, providing a valuable tool for condition assessment.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115642"},"PeriodicalIF":3.0,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836694","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}
Biodegradable polymers such as poly(glycolic acid) (PGA) and poly(lactic acid) (PLA) are widely used in biomedical applications due to their biocompatibility and tunable degradation behavior. Here, a combined Density Functional Theory (DFT) and Machine Learning (ML) framework is employed to investigate the structural and electronic properties of Curcumin–polymer complexes. Geometries were optimized at the B3LYP/6-311++G(d,p) level, and frontier-orbital descriptors were refined using ωB97X-D single-point calculations. ESP mapping shows that Curcumin–PGA exhibits a broader potential range than Curcumin–PLA, indicating stronger electrostatic polarization. FMO analysis reveals a pronounced contrast in electronic response: Curcumin–PGA displays a significantly reduced HOMO–LUMO gap (2.52 eV), whereas Curcumin–PLA retains a much larger gap (6.86 eV). AIM analysis confirms medium-strength hydrogen bonding. ML modeling, used qualitatively due to the small dataset, identifies ΔEgap and ESP range as dominant descriptors of degradation behavior. This integrated DFT–ML approach clarifies Curcumin–polymer interactions and supports rational design of biodegradable drug-delivery systems.
{"title":"Computational investigation of curcumin–polymer interactions: a DFT–ML integrated framework for electronic structure and biodegradation analysis of PGA and PLA complexes","authors":"Mohammad Rizehbandi , Hadise Nobakht , Neda Jannesar , Negar Yousefi","doi":"10.1016/j.comptc.2025.115641","DOIUrl":"10.1016/j.comptc.2025.115641","url":null,"abstract":"<div><div>Biodegradable polymers such as poly(glycolic acid) (PGA) and poly(lactic acid) (PLA) are widely used in biomedical applications due to their biocompatibility and tunable degradation behavior. Here, a combined Density Functional Theory (DFT) and Machine Learning (ML) framework is employed to investigate the structural and electronic properties of Curcumin–polymer complexes. Geometries were optimized at the B3LYP/6-311++G(d,p) level, and frontier-orbital descriptors were refined using ωB97X-D single-point calculations. ESP mapping shows that Curcumin–PGA exhibits a broader potential range than Curcumin–PLA, indicating stronger electrostatic polarization. FMO analysis reveals a pronounced contrast in electronic response: Curcumin–PGA displays a significantly reduced HOMO–LUMO gap (2.52 eV), whereas Curcumin–PLA retains a much larger gap (6.86 eV). AIM analysis confirms medium-strength hydrogen bonding. ML modeling, used qualitatively due to the small dataset, identifies ΔEgap and ESP range as dominant descriptors of degradation behavior. This integrated DFT–ML approach clarifies Curcumin–polymer interactions and supports rational design of biodegradable drug-delivery systems.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115641"},"PeriodicalIF":3.0,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836697","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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