Chemical Physics最新文献

{"title":"Selective adsorption, structure and dynamics of CO2 – CH4 mixture in Mg-MOF-74 and the influence of intercrystalline disorder","authors":"I. Dhiman ,&nbsp;David R. Cole ,&nbsp;Siddharth Gautam","doi":"10.1016/j.chemphys.2025.112661","DOIUrl":"10.1016/j.chemphys.2025.112661","url":null,"abstract":"<div><div>Mg-MOF-74 is a highly efficient adsorbent for CO₂. We use molecular simulations to study the effects of disorder in Mg-MOF-74 on the selective adsorption, structure, and dynamics of a CO₂-CH₄ mixture. Positional disorder is introduced in the adsorbent by separating individual Mg-MOF-74 crystallites via inserting intercrystalline space between them. Rotating a crystallite with respect to others by different extents provides the orientational disorder (OD). Disorder is observed to enhance the adsorption selectivity of CO₂ over CH₄. The additional adsorption sites available by exposing crystallite surfaces may provide added selectivity for CO₂. Disorder is found to affect both the translational as well as rotational motion of CO₂ in Mg-MOF-74. This behavior follows a systematic pattern dictated by the interplay of the pore geometry of Mg-MOF-74 and Mg²⁺ − CO₂ interactions. Our results provide a guide on how to tailor Mg-MOF-74 adsorption behavior with desired properties by purposeful introduction of disorder.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"594 ","pages":"Article 112661"},"PeriodicalIF":2.0,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Implementation of DMET-CCSD(T) in Water Clusters: Reduced Scaling and Quality of Relative Energies","authors":"Yi Sun","doi":"10.1016/j.chemphys.2025.112640","DOIUrl":"10.1016/j.chemphys.2025.112640","url":null,"abstract":"<div><div>We present a method to significantly reduce the computational scaling of the post-Hartree–Fock (post-HF) component in Density Matrix Embedding Theory (DMET) calculations by exploiting the exponential decay properties of both the mean-field density matrix and the orbital transformation matrix. Additionally, we extend this reduced-scaling approach to calculate the coupled-cluster CCSD(T) density matrix, facilitating DMET-CCSD(T) energy evaluations through a back-transformed energy formula. The accuracy of relative electronic energies is benchmarked using the all-electron solver, Lowdin-partitioned fragments, and fragments derived from Intrinsic Atomic Orbital and Projected Atomic Orbital (IAO+PAO) partitioning schemes. Our results demonstrate that, with appropriate utilization of the decay of one particle density matrix (1-PDM), the scaling in the evaluation of the post-HF energy can be reduced. Furthermore, for relative electronic energies calculations, Lowdin partitioning performs well in weakly interacting systems, such as water clusters. This study underscores the potential of reduced-scaling techniques to improve computational efficiency and the efficacy of CCSD(T) solvers in delivering accurate thermochemical predictions in weakly interacting systems.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112640"},"PeriodicalIF":2.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421448","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":"Interaction of lanthanum oxide and molten fluoride system FLiNaK: In situ Raman experiment and density functional theory simulations","authors":"Irina Zakiryanova,&nbsp;Dmitry Zakiryanov","doi":"10.1016/j.chemphys.2025.112659","DOIUrl":"10.1016/j.chemphys.2025.112659","url":null,"abstract":"<div><div>Molten mixture of alkali metal fluorides FLiNaK is a promising coolant for molten salt nuclear reactors. The presence of oxygen-containing impurities can lead to corrosion, degradation and destruction of structural materials. This paper presents the results of studying the mechanism of the interaction of the molten FLiNaK with lanthanum oxide by <em>in situ</em> Raman spectroscopy and <em>ab initio</em> molecular dynamics (AIMD) simulations. High-temperature Raman studies supplemented by the results of XRD analysis and thermodynamic modeling reveal an irreversible heterogeneous reaction La₂O₃(s) + 2 LiF(sol) → 2 LaOF(s) + Li₂O(sol). When the temperature increases, the LaOF dissolves. Additionally, the kinetics of interaction of La₂O₃ with water vapor in the air atmosphere was studied. AIMD data concur closely with the experimental results: we identified formation of the intermediate range order structures containing oxygen, lanthanum, lithium and fluorine ions with the O<img>Li coordination number being 1.92.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112659"},"PeriodicalIF":2.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422012","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":"Physical mechanism of nonlinear optical properties in Lemniscular carbon nanohoops","authors":"Yunyun Ren ,&nbsp;Xinwen Gai ,&nbsp;Jingang Wang ,&nbsp;Lijuan Wang","doi":"10.1016/j.chemphys.2025.112655","DOIUrl":"10.1016/j.chemphys.2025.112655","url":null,"abstract":"<div><div>In this study, the properties of orbital energy levels, one-photon absorption (OPA) spectrum, two-photon absorption (TPA) spectrum, Raman spectrum, pre-resonance Raman spectrum, and electronic circular dichroism (ECD) spectrum of all‑carbon lemniscular nanohoops bis-pm-TC and bis-po-CC were systematically investigated using density functional theory (DFT) and wavefunction analysis. The transition properties of electrons in the excited states were analyzed through charge density difference (CDD) and transition density matrix (TDM) visualization methods, offering insights into the physical mechanisms of intramolecular charge transfer. Additionally, the Raman spectral responses to excitation light of different wavelengths were calculated. The ECD spectrum revealed distinct chiralities for bis-pm-TC and bis-po-CC, which were further explained by analyzing the densities and orientations of their transition electric dipole moments (TEDMs) and magnetic dipole moments (TMDMs).</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112655"},"PeriodicalIF":2.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421447","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":"Tunable electronic and optical properties of CdO/ZrS2 heterostructure based on first principles","authors":"Peijie Cheng ,&nbsp;Xing Wei ,&nbsp;Zhuangzhuang Dai ,&nbsp;Yan Zhang ,&nbsp;Yun Yang ,&nbsp;Jian Liu ,&nbsp;Ye Tian ,&nbsp;Li Duan","doi":"10.1016/j.chemphys.2025.112654","DOIUrl":"10.1016/j.chemphys.2025.112654","url":null,"abstract":"<div><div>In this research, the first-principles calculations based on the density functional theory (DFT) is used to work on and to tune the geometric configuration, optical characteristic, and electronic performance of the CdO/ZrS₂ heterostructure. The results reveal that the CdO/ZrS₂ heterostructure is a Type-II van der Waals heterojunction (vdWH). It is detected that the Type-II CdO/ZrS₂ heterojunction of a layer distance of 3.04 Å has the most stable structure with a direct bandgap of 0.3311 eV. The bandgap value of the heterojunction is smaller than the bandgaps of the two monolayers, which benefits the separation of photogenerated carriers. The transformation of a semiconductor into a metal can emerge by way of both the utilization of an external applied electric field and the imposition of strain. Under the utilization of the external electric fields and biaxial strain, the heterojunction reserves a Type-II band arrangement. By applying biaxial strain of 6 %, the increase of Eg reaches its maximum value of 0.9549 eV, and the heterojunction shows a transition from direct-gap to indirect-gap. The use of an external applied electric field and the imposition of strain can improve the light absorption coefficient of the heterojunction, making the absorption spectra of the heterostructure to exhibit a blue or red shift, which adjusts the optical properties of the heterojunction. There are expectations that this research can furnish theoretical reference value for pertinent experiments and assistance for the heterostructure in the new generation of optoelectronic materials.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112654"},"PeriodicalIF":2.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429072","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":"Structure unit group (SUG)-perturbed Gaussian basis sets used in Hartree-Fock calculation for molecules consisted of atoms (H, C, N, O)","authors":"Tong-Hyok Cha ,&nbsp;Gum-Chol Kim ,&nbsp;Kwang-Jin Ri ,&nbsp;Yong-Su Pak","doi":"10.1016/j.chemphys.2025.112653","DOIUrl":"10.1016/j.chemphys.2025.112653","url":null,"abstract":"<div><div>Four Gaussian basis sets (6-31G(d,p), cc-pVDZ, DGDZVP, Ahlrichs-pVDZ) similar in their contraction patterns are perturbed in various structure unit groups (SUGs) [Chem. Phys. 570(2023) 111890] comprised of atoms including H, C, N or O. All SUG-perturbed sets are subsequently stored in a database “SUG-GP” and applied to Hartree-Fock (HF) calculation. Under the SUG-perturbation, except for contracted Gaussian type orbitals (GTOs), all the primitive GTOs in former two sets are almost the same. The primitive GTO-exponents in former three sets are almost similar with each other. The SUG-perturbed sets generally yield the lower HF-energies and better Virial ratios than originals.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112653"},"PeriodicalIF":2.0,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429071","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":"Aluminum-doped T-graphene: An innovative platform for enhanced sensitivity in hydrogen cyanide detection","authors":"Mounir M. Bekhit ,&nbsp;Mustafa Mudhafar ,&nbsp;Zainab Ahmed Abass ,&nbsp;Prakash Kanjariya ,&nbsp;Suhas Ballal ,&nbsp;Abhayveer Singh ,&nbsp;Pushpa Negi Bhakuni ,&nbsp;Zainab Jamal Hamoodah ,&nbsp;Fawaz Almutairi","doi":"10.1016/j.chemphys.2025.112648","DOIUrl":"10.1016/j.chemphys.2025.112648","url":null,"abstract":"<div><div>This study investigates the effectiveness of pristine and aluminum-doped T-graphene (TG) nanosheets as hydrogen cyanide (HCN) sensors. Al doping modifies the electronic characteristics and reactivity of the TG, dramatically enhancing their sensing capabilities. Al-TG demonstrates a strong affinity for HCN (−16.6 kcal·mol⁻¹) and a significant alteration in the HOMO-LUMO energy gap, measured at 13.7 %. This nanostructure exhibits a commendable recovery time of only 1.6 s, a key factor for real-time, on-site detection. This rapid recovery, combined with the strong binding affinity, makes Al-doped TG a promising candidate for developing highly sensitive and responsive HCN sensors. Natural bond orbital analysis emphasizes the critical role of charge transfer during adsorption. Furthermore, atoms in molecules analysis categorizes the nature of these interactions as partially covalent. These results pave the way for developing practical, portable, and cost-effective HCN sensors for diverse applications, ranging from industrial safety monitoring to environmental protection.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112648"},"PeriodicalIF":2.0,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421449","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":"Functional groups optimization at molecular-scale to improve polyamine treatment agent performance on sodium bentonite surface hydration inhibition under high-temperature/high-pressure failure","authors":"Justine Kiiza ,&nbsp;Jiafang Xu","doi":"10.1016/j.chemphys.2025.112649","DOIUrl":"10.1016/j.chemphys.2025.112649","url":null,"abstract":"<div><div>Application of water-based drilling mud systems poses challenges of wellbore instability due to overhydration and dispersion of contained Na-bentonite/montmorillonite (Na-Mnt), which readily experience hydration expansion, dispersing into the drilling fluids, reducing their performance. Alkylamine-organoclays' inhibition ability of Na-Mnt surface hydration weakens under deeper wellbore harsh conditions, degrading the drilling fluid performance. Functional groups are indispensable for the performance of organic inhibitors, thus keen selection of functional groups is necessary to improve inhibition action. The effect of aminomethyl, hydroxymethyl, ethyl, and <em>N</em>,<em>N</em>-dimethylacetamidomethyl functional groups on the inhibition of heptane-1,7-diamine and intermolecular interactions in the Mnt outer surface hydration system were investigated under high-temperature/high-pressure (HT/HP) using molecular dynamics simulation. Adsorption conformation, H-bond formation, hydration analysis, self-diffusivity, and interaction energy parameters were scrutinised. <em>N</em>,<em>N</em>-dimethylacetamidomethyl showed the best surface hydration inhibition improvement. HT/HP significantly reduced the inhibition effectiveness. This study conceptualizes the development of alkylamine-bentonite-based drilling fluid additives for deep and ultra-deep wellbore stabilisation.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"594 ","pages":"Article 112649"},"PeriodicalIF":2.0,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488955","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":"Electron-donating substituents allow boosted fluorescence emission wavelengths of Dihydropyridopyrazine functionalized xanthene","authors":"Caidong Shuang,&nbsp;Chong Chang,&nbsp;Pingping Sun,&nbsp;Chaoyuan Zeng,&nbsp;Weijie Chi","doi":"10.1016/j.chemphys.2025.112641","DOIUrl":"10.1016/j.chemphys.2025.112641","url":null,"abstract":"<div><div>Fluorescent dyes are pivotal tools in biological imaging, environmental sensing, and biomedicine. Long-wavelength dyes, particularly those in the second near-infrared (NIR-II) region, are highly sought after for their enhanced fluorescence quantum yields, excellent photostability, and broad chemical tunability. Despite their potential, systematic strategies for designing such dyes remain limited. In this work, we present an effective approach for extending the emission wavelengths of xanthene-based dyes by replacing the bridging oxygen atom in the heteroanthracene core with various substituents, including -C(CH₃)₂, -Si(CH₃)₂, and -P(<em>O</em>)Ph. These modifications yielded three xanthene-based derivatives with promising NIR-II fluorescence. Theoretical calculations were employed to investigate the structural and electronic properties of the four dyes. Our results reveal that the phosphorus oxide substitution led to a remarkable fluorescence emission at 1864 nm. These findings provide important insights into the design principles for developing second near-infrared fluorescent dyes with potential applications in advanced imaging and sensing technologies.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112641"},"PeriodicalIF":2.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379335","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":"Adsorption of indoor hazardous gases on Zn and ZnO modified MoS2 monolayers: A first-principles study","authors":"Jiantao Yin ,&nbsp;Yipeng Chen ,&nbsp;Yanhui Liu ,&nbsp;Fengxing Jiang ,&nbsp;Huanhuan Qiu ,&nbsp;Rongri Tan","doi":"10.1016/j.chemphys.2025.112634","DOIUrl":"10.1016/j.chemphys.2025.112634","url":null,"abstract":"<div><div>The detection of indoor hazardous gases is crucial for safeguarding human health, while MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> shows great potential in absorbing harmful indoor gases. However, the adsorption performance of MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> monolayer is still very limited. In this study, first-principles theoretical calculations are employed to investigate the adsorption performance of Zn and ZnO modified MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> towards NH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>, HCHO and C<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>. We systematically examined the thermal stability, gas adsorption mechanisms and practical application potential of three modified MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> (Zn-MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, ZnO-MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> and ZnO+Zn-MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>). The results reveal that modified MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> exhibits excellent conductivity and gas adsorption capabilities. Specifically, both ZnO-MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> and ZnO+Zn-MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> exhibit strong chemisorption with the HCHO molecule, demonstrating adsorption energies of -1.915 eV and -1.985 eV, respectively. Furthermore, when the temperature reaches 348 K, ZnO-MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> shows high sensitivity (249%) and excellent recovery capability (4.2 S) towards C<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>, indicating its potential advantages in the development of recyclable C<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>H<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span> sensors. This research provides theoretical insights into utilizing MoS<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>-based sensors for detecting indoor hazardous gases.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"593 ","pages":"Article 112634"},"PeriodicalIF":2.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403153","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}