Computational and Theoretical Chemistry最新文献

{"title":"The Structural, Elastic, and thermodynamic properties of Sr2P7Br Double Zintl salt with heptaphosphanortricyclane configuration","authors":"Missoum Radjai ,&nbsp;Saber Saad Essaoud ,&nbsp;Abdelmadjid Bouhemadou ,&nbsp;Djamel Allali ,&nbsp;Abdelhak Bedjaoui","doi":"10.1016/j.comptc.2024.114947","DOIUrl":"10.1016/j.comptc.2024.114947","url":null,"abstract":"<div><div>We investigated the effects of externally applied pressure on the Sr₂P₇Br compound’s properties, specifically its crystalline structure, elasticity, and thermodynamics. This investigation was carried out using the pseudopotential plane wave method within the framework of density functional theory. We used the well-known PBEsol variant of the exchange–correlation general gradient approximation specifically designed for solid-state analysis. This is the first endeavor to investigate the effects of pressure on the Sr₂P₇Br material using a theoretical approach. The computed equilibrium structural parameters closely match the relevant experimental counterpart values. The determined elastic constants, obtained under both ambient pressure and hydrostatic pressures up to 18 GPa, satisfy the mechanical stability requirements. Based on the computed Pugh’s ratio, Cauchy pressure, and Poisson’s ratio, it can be concluded that the Sr₂P₇Br compound exhibits ductile behavior. The polycrystalline elastic moduli, including the isotropic bulk modulus, shear modulus, Young’s modulus, and Poisson’s ratio, at ambient pressure and under pressure effects, were derived from the single-crystal elastic constants. Additionally, associated parameters, such as average sound velocity, Debye temperature, minimum thermal conductivity, and Vickers hardness, were examined under pressure influences. The quasi-harmonic Debye approximation was used to investigate the relationship between temperature and some macroscopic physical parameters, such as lattice parameter, bulk modulus, Debye temperature, volume thermal expansion coefficient, and isobaric and isochoric heat capacities, at fixed pressures of 0, 4, 8, 12, and 16 GPa. The results derived from the elastic constants exhibit substantial concordance with those computed using the Debye quasi-harmonic model, thereby validating the reliability of our findings.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114947"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657638","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":"Carborazine doped nanographene (CBNG) sheet as a promising NO2 gas sensor: A theoretician’s approach","authors":"Subhadip Ghosh,&nbsp;Prasanta K. Nandi","doi":"10.1016/j.comptc.2024.114977","DOIUrl":"10.1016/j.comptc.2024.114977","url":null,"abstract":"<div><div>Nanographenes (NGs) are a distinct section of graphene in which the dangling bonds are saturated with hydrogen atoms (C₄₂H₁₈). This confinement in size results in unique properties and potential applications. The density functional theory (DFT) is used to investigate the reactivity and electronic sensitivity of a model carborazine (B₂C₂N₂) ring doped nanographene (CBNG) for detecting NO₂ gas. In CBNG/NO₂ complex, one oxygen atom of the NO₂ molecule is positioned at a distance of 2.93Ả from the center of the B₂C₂N₂ ring, with an adsorption energy −6.2 kcal/mol. The adsorption energy of NO₂ on CBNG is apparently larger than those of other gas molecules, which fall between the suitable range of strong physical adsorption and weak chemical adsorption. Upon NO₂ adsorption, the band gap of CBNG sheet reaches 62.4 %. The outcome of the present study may be exploited in the industry, particularly in the synthesis of effective NO₂ gas sensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114977"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-principles study of sodium adsorption and diffusion over substitutionally doped phosphorene","authors":"Sneha Upadhyay ,&nbsp;Pankaj Srivastava","doi":"10.1016/j.comptc.2024.114955","DOIUrl":"10.1016/j.comptc.2024.114955","url":null,"abstract":"<div><div>Phosphorene, due to its remarkable semiconducting properties, prevailed as principal material of research for decades. The substitutional doping of carbon (C), silicon (Si), oxygen (O) and sulphur (S) atom was reported earlier. DFT studies are done towards the unexplored area of sodium (Na) adsorption and diffusion over these doped phosphorene structures. The effective adsorption energies for C-, Si-, O- and S- doped phosphorene are −3.19 eV, −2.63 eV, −3.12 eV and −2.39 eV respectively. The minimum value of activation energies are 0.68 eV, 0.45 eV, 1.00 eV and 0.26 eV respectively. Hence the diffusion and intercalation–deintercalation process seem to be supportive. The lattice integrity is maintained in the whole process. Good amount of charge transfer shows better conductivity supported by band structure and density of states diagrams. Based on these data, the proposed doped phosphorene configurations can be predicted suitable for further studies towards anode application in Na-ion battery.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114955"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657635","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":"Comparing the linear and non-linear optical properties of keto-enol forms of N-alkyl, N-aryl, and O-alkyl substituted 2-Hydroxybenzophenone","authors":"Zeba Khan,&nbsp;Nagaiyan Sekar","doi":"10.1016/j.comptc.2024.114980","DOIUrl":"10.1016/j.comptc.2024.114980","url":null,"abstract":"<div><div>The Geometrical, electronical, spectral, linear, and non-linear optical properties (NLO) of keto-enol forms of 2-hydroxybenzophenone (2-HBp) derivatives were examined. Ten pairs of 2-HBp derivatives having D-π-A framework with <em>N</em>-alkyl (ethyl, julolidine), <em>N</em>-aryl (phenyl), O-methyl, groups as donor, phenyl ring as a<!--> <!-->spacer, and carbonyl group linked to phenyl ring consisting of either mono or dicarboxylic acid group as acceptor, were selected. DFT results suggest that<!--> <!-->the keto form is stable<!--> <!-->in the S₀ and S₁ states. Further, IR spectra, CV analysis, experimental absorption maxima, and TD-DFT results support the existence of 2-HBp derivatives in keto form. Thermogravimetric analysis shows that 2-HBp derivatives have remarkable thermal stability (∼200 °C), enabling their practical application in NLO. Further, DFT and TD-DFT results show that the<!--> <!-->keto form of 2-HBp derivatives with lower BLA, higher μ, ω, η, Γ, and hyperpolarizability exhibits superior NLO properties compared to the<!--> <!-->enol form of 2-HBp derivatives.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114980"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657634","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":"Halogen substitution effects in Chlorostannate(II) hybrid material: Insights from DFT study on 2(C4H4FN3O)·SnX6·2(H2O), (X = F, Cl, Br, I)","authors":"Rim Bechaieb ,&nbsp;Maha F. El-Tohamy ,&nbsp;Gamal A.E. Mostafa","doi":"10.1016/j.comptc.2024.114978","DOIUrl":"10.1016/j.comptc.2024.114978","url":null,"abstract":"<div><div>The development of new materials is crucial for advancing technologies in material science, energy, and biology. In this study, we investigate the effect of Halogen-substitution on the compound 2(C₄H₄FN₃O)·SnX₆·2(H₂O) (where X = F, Cl, Br, and I). Using extensive theoretical analysis, we examined the impact of halogen substitution on the structural properties, band gap energy (Eg), and chemical behavior. Our results show that the Eg decreases with the increasing atomic number of halogens. The I-substituted compound is the most reactive and exhibits significant intramolecular charge transfer, enhancing its antioxidant properties. The spatial distribution of electron density in the Frontier Molecular Orbitals (FMOs) indicates that the HOMO is localized on the inorganic anion and the LUMO on the organic cation, a pattern consistent across all substituted compounds. These findings highlight the potential of these compounds in electron transfer reactions and provide insights for tailoring them for specific chemical and biochemical applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114978"},"PeriodicalIF":3.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657670","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":"Exploring the covalent inhibition mechanisms of inhibitors with two different warheads acting on SARS-CoV-2 Mpro by QM/MM simulations","authors":"Xiaoyue Yang ,&nbsp;Mengguo Chen ,&nbsp;Fanru Yuan ,&nbsp;Jiangnan Zhang ,&nbsp;Jinshuai Song ,&nbsp;Longhua Yang","doi":"10.1016/j.comptc.2024.114979","DOIUrl":"10.1016/j.comptc.2024.114979","url":null,"abstract":"<div><div>SARS-CoV-2 M^pro had been reported to react with covalent inhibitors <strong>14c</strong> and <strong>C7</strong>, containing a vinyl sulfanilamide and chloromethylamide as the warheads, respectively. However, the detailed reaction mechanisms and warhead effects are still unclear. In this study, the initial state of the catalytic dyad Cys145/His41 is determined as neutral during the non-covalent binding, through MM-PBSA free energy calculations. The Potential of Mean Forces (PMFs) have been computed by QM/MM MD method, obtaining the free energy changes from reactants to products. Both reactions follow asynchronous mechanism. Except the similar proton transfer (PT1), subsequently, nucleophilic addition and an additional proton transfer (PT2) for <strong>14c</strong>, while an S_N2 nucleophilic substitution for <strong>C7</strong> are underwent, respectively. The reaction activation barrier and free energy trends both are in consistent with the experimental IC₅₀ results. Our research enhances understanding of the inhibitory mechanism, and provides insights for designing novel and more effective inhibitors targeting SARS-CoV-2 M^pro.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114979"},"PeriodicalIF":3.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First-principle’s calculations to investigate structural, electronic, mechanical, optical, and thermoelectric properties of halide double perovskites K2InScX6 (X = Cl, Br, and I) for thermoelectric and optoelectronic applications","authors":"M. Shakil ,&nbsp;Sania Maqsood ,&nbsp;M. Mudassir ,&nbsp;M. Asghar Gadhi ,&nbsp;S.S. Gillani ,&nbsp;Islam H. El Azab","doi":"10.1016/j.comptc.2024.114970","DOIUrl":"10.1016/j.comptc.2024.114970","url":null,"abstract":"<div><div>Physical properties of double perovskites K₂InScX₆ (X = Cl, Br, and I) are investigated using density functional theory (DFT) with generalized gradient approximation (GGA) and perdew-burke-ernerhof (PBE) exchange co-relational functional. Structural stability is confirmed through geometry optimization. Band gaps are calculated using Trans Blaha-modified Becke-Johnson (TB-mBJ) potential and GGA-PBE methods. The obtained band gaps have direct nature. The structural stability has also been confirmed by calculating enthalpy formation (ΔH_f), cohesive energy (E_coh), stiffness coefficients (C_ij), tolerance (τ_G) and octahedral factor (µ). Two materials K₂InScCl₆, and K₂InScBr₆ are ductile and one is K₂InScI₆ brittle. The optical parameters inferred that the maximum absorption of photon energy lies within the visible and ultraviolet regions enabling their use in UV photodetectors and optoelectronics, where light absorption is important for performance. The thermoelectric (TE) parameters like Seebeck coefficient, thermal and electrical conductivity, carrier concentration, power factor and figure of merit ZT parameters are calculated and ZT values are 0.75, 0.94, and 0.91 for K₂InScCl₆, K₂InScBr₆, and K₂InScI₆ at room temperature. These results enable the development of more stable, and high-conversion efficiency devices for TE applications such as thermo-electric power generators.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114970"},"PeriodicalIF":3.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the mechanism of reverse saturable absorption in zinc tetrapyridyl porphyrins","authors":"Xianghao Sun,&nbsp;Hongjuan Zhu,&nbsp;Shifeng Qian,&nbsp;Xiaowei Sheng","doi":"10.1016/j.comptc.2024.114946","DOIUrl":"10.1016/j.comptc.2024.114946","url":null,"abstract":"<div><div>Reverse saturable absorption (RSA) is one of the important mechanism for a molecule showing optical-limiting property. The experiment found that zinc tetrapyridyl porphyrins (ZnTPyP) exhibit distinct RSA characteristics at both 470 nm and 532 nm wavelengths. To understand the origin of the RSA in ZnTPyP, a theoretical analysis based on the linear-response time-dependent density functional theory(LR-TDDFT) for the ground state absorption (GSA) and the pseudo-wavefunction formulation of LR-TDDFT(PWF-TDDFT) for excited states absorption (ESA) were conducted. Experimentally observed RSA in ZnTPyP are well predicted. It is shown that the transitions of <span><math><mrow><msub><mrow><mi>S</mi></mrow><mrow><mn>1</mn></mrow></msub><mo>→</mo><msub><mrow><mi>S</mi></mrow><mrow><mn>13</mn><mo>,</mo><mn>14</mn><mo>,</mo><mn>15</mn><mo>,</mo><mn>18</mn></mrow></msub></mrow></math></span> are the origin of the observed RSA feature in ZnTPyP. We found that these excited states transitions exhibit intramolecular charge transfer character and the pyridyl groups play an important role in the charge transfer process. It is also noticed that the pyridyl groups results in a red shift for both the GSA and ESA of porphyrin. In addition, the central zinc atom causes the energy gap between the positions with prominent absorption in GSA and ESA increased. These observations indicate that pyridyl groups and central zinc atom play an important role in tuning the spectral window and strength of RSA in the porphyrin complexes. These observations provide guidance for designing novel optical-limiting materials based on the porphyrin derivatives.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114946"},"PeriodicalIF":3.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657671","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":"Molecular electronic structure calculation via a quantum computer","authors":"Hamid Reza Naeij ,&nbsp;Erfan Mahmoudi ,&nbsp;Hossein Davoodi Yeganeh ,&nbsp;Mohsen Akbari","doi":"10.1016/j.comptc.2024.114945","DOIUrl":"10.1016/j.comptc.2024.114945","url":null,"abstract":"<div><div>Quantum computers can be used to calculate the electronic structure and estimate the ground state energy of many-electron molecular systems. In the present study, we implement the Variational Quantum Eigensolver (VQE) algorithm, as a hybrid quantum–classical algorithm to calculate the ground state energy of the molecules such as H<span><math><msubsup><mrow></mrow><mrow><mn>3</mn></mrow><mrow><mo>+</mo></mrow></msubsup></math></span>, OH<span><math><msup><mrow></mrow><mrow><mo>−</mo></mrow></msup></math></span>, HF and BH<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> in which the number of qubits has an increasing trend. We use the parity transformation for fermion to qubit encoding and the Unitary Coupled Cluster for Single and Double excitations (UCCSD) to construct an ansatz. We compare our quantum simulation results with the computational chemistry approaches including Full Configuration Interaction (FCI), as benchmark energy and Unrestricted Hartree–Fock (UHF), as a common computational method. Our results show that there is a good agreement between molecular ground state energy obtained from VQE and FCI. Moreover, the accuracy of the ground state energies obtained from VQE in our work is higher than the previously reported values. This work aims to benchmark the VQE algorithm to calculate the electronic ground state energy for a new set of molecules that can be good candidates for molecular simulation on a real quantum computer.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114945"},"PeriodicalIF":3.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657669","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":"Enhanced performance of a promising Au/TMDC heterostructure composed of MoTe2 nanosheets decorated with Au5 clusters: A DFT study","authors":"Esmail Vessally ,&nbsp;Rovnag Rzayev ,&nbsp;Bayan Azizi ,&nbsp;Pawan Sharma ,&nbsp;Abhishek Kumar","doi":"10.1016/j.comptc.2024.114933","DOIUrl":"10.1016/j.comptc.2024.114933","url":null,"abstract":"<div><div>This research uses density functional theory approach combined with the spin–orbit coupling to study how the SO_x molecules stick to Au₅ cluster functionalized MoTe₂ nanosheets. In fact, the promising Au/MoTe₂ heterostructure system is constructed to model the attachment of gases on its surface. The high efficiency of adsorption process is evident from the strong sticking of the SO_x to the Au atoms. Both Au₁ and Au₅ cluster modified MoTe₂ nanosheets revealed semiconducting feature, and in Au₅ cluster modified system, the band gap narrowed, while the conductivity is enhanced. Thus, results showed that adding Au cluster to the MoTe₂ made it best for adsorbing gases, while MoTe₂ without any additives absorbed the gases weakly. The conductivity and recovery time are also analyzed to further describe the results. Based on our theoretical consequences, the Au₅ cluster functionalized MoTe₂ (Au_/MoTe₂ heterostructure system) seem good for constructing innovative sensors to detect SO_x molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114933"},"PeriodicalIF":3.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657637","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}