Pub Date : 2024-03-15DOI: 10.1007/s00214-024-03098-w
Abstract
This study investigates the supramolecular interactions between perylene diimides (PDI) and nucleotides, specifically adenosine monophosphate (AMP) and cytidine monophosphate (CMP). Ten complexes (complex 1 (l-ala-PDI-AMP), complex 2 (B-ala-PDI-AMP), complex 3 (GLY-PDI-AMP), complex 4 (IMI-PDI-AMP), complex 5 (PYR-PDI-AMP, complex 6 (l-ala-PDI-CMP), complex 7 (B-ala-PDI-CMP), complex 8 (GLY-PDI-CMP), complex 9 (IMI-PDI-CMP), and complex 10 (PYR-PDI-CMP), were simulated using the B3LYP/6-31G(d,p) level of DFT method. The study explores NMR, IR, UV, hyperpolarizabilities, frontier molecular orbitals (FMOs), density of states (DOS), noncovalent interactions (NCI), iso-surface analysis, atom in molecule (AIM), dipole moment (µ), electron density distribution map (EDDM), transition density matrix (TDM), molecular electrostatic potential (MEP), and electron–hole analysis (EHA) using differential functional theory (DFT). The weak bonds formed were visualized using Discovery Studio Visualizer. The electronic properties of the complexes were examined through natural bond orbital (NBO) and natural population analysis (NPA), leading to nonlinear optics (NLO) study. Complex 6 demonstrates the highest NLO activity with γ static of 17,424,700.00, and complex 10 exhibits the weakest NLO activity with second dipole hyperpolarizability (γ static) at 25,116.10. Moreover, global reactivity factors for complexes 1–5 show EA ranging from 6.53 to 7.7, and ionization potential (IP) spans 7.8–8.8. Global hardness values highlight complex 4 as the hardest (η = 0.55) and complex 1 as the softest (η = 0.51). Electronegativity (X) varies from 7.28 to 8.25, with complex 3 being the most electronegative. Chemical potential (μ) ranges from − 7.9 to − 8.25, global softness (σ) identifies complex 1 as the softest (0.2575) and complex 4 as the hardest (0.435). Electrophilicity (ω) ranges from 33.30 to 61.87. Complexes 6–10 show EA from 6.7 to 7.53. IP values range from 8.4 to 8.6, with complexes 7 and 10 highest. Global hardness spans 0.53 to 0.85. X ranges from 7.55 to 8.06, with complex 7 the most electronegative. μ varies from − 7.55 to − 8.06, and complex 7 has the lowest. From σ values, complexes 9 and 10 are the softest. ω ranges from 35.53 to 60.78, with complex 7 the most electrophilic.
{"title":"Exploring nonlinear optical properties of perylene diimide and biomolecules complexes: a computational supramolecular study","authors":"","doi":"10.1007/s00214-024-03098-w","DOIUrl":"https://doi.org/10.1007/s00214-024-03098-w","url":null,"abstract":"<h3>Abstract</h3> <p>This study investigates the supramolecular interactions between perylene diimides (PDI) and nucleotides, specifically adenosine monophosphate (AMP) and cytidine monophosphate (CMP). Ten complexes (complex 1 (<span>l</span>-ala-PDI-AMP), complex 2 (B-ala-PDI-AMP), complex 3 (GLY-PDI-AMP), complex 4 (IMI-PDI-AMP), complex 5 (PYR-PDI-AMP, complex 6 (<span>l</span>-ala-PDI-CMP), complex 7 (B-ala-PDI-CMP), complex 8 (GLY-PDI-CMP), complex 9 (IMI-PDI-CMP), and complex 10 (PYR-PDI-CMP), were simulated using the B3LYP/6-31G(d,p) level of DFT method. The study explores NMR, IR, UV, hyperpolarizabilities, frontier molecular orbitals (FMOs), density of states (DOS), noncovalent interactions (NCI), iso-surface analysis, atom in molecule (AIM), dipole moment (<em>µ</em>), electron density distribution map (EDDM), transition density matrix (TDM), molecular electrostatic potential (MEP), and electron–hole analysis (EHA) using differential functional theory (DFT). The weak bonds formed were visualized using Discovery Studio Visualizer. The electronic properties of the complexes were examined through natural bond orbital (NBO) and natural population analysis (NPA), leading to nonlinear optics (NLO) study. Complex 6 demonstrates the highest NLO activity with γ static of 17,424,700.00, and complex 10 exhibits the weakest NLO activity with second dipole hyperpolarizability (γ static) at 25,116.10. Moreover, global reactivity factors for complexes 1–5 show EA ranging from 6.53 to 7.7, and ionization potential (IP) spans 7.8–8.8. Global hardness values highlight complex 4 as the hardest (<em>η</em> = 0.55) and complex 1 as the softest (<em>η</em> = 0.51). Electronegativity (X) varies from 7.28 to 8.25, with complex 3 being the most electronegative. Chemical potential (<em>μ</em>) ranges from − 7.9 to − 8.25, global softness (<em>σ</em>) identifies complex 1 as the softest (0.2575) and complex 4 as the hardest (0.435). Electrophilicity (<em>ω</em>) ranges from 33.30 to 61.87. Complexes 6–10 show EA from 6.7 to 7.53. IP values range from 8.4 to 8.6, with complexes 7 and 10 highest. Global hardness spans 0.53 to 0.85. <em>X</em> ranges from 7.55 to 8.06, with complex 7 the most electronegative. μ varies from − 7.55 to − 8.06, and complex 7 has the lowest. From <em>σ</em> values, complexes 9 and 10 are the softest. <em>ω</em> ranges from 35.53 to 60.78, with complex 7 the most electrophilic.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140155317","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-13DOI: 10.1007/s00214-024-03100-5
Ingrid Jelemenska, Michal Zalibera, Peter Rapta, Anatoly A. Dobrov, Vladimir B. Arion, Lukas Bucinsky
The anti (a) to syn (s) isomerization pathway of the deprotonated form of the dimer with two nickel(II) 15-membered octaazamacrocyclic units connected via a carbon–carbon (C–C) σ bond was investigated. For the initial anti (a) structure, a deprotonation of one of the bridging (sp3 hybridized) carbon atoms is suggested to allow for an a to s geometry twist. A 360° scan around the bridging C–C dihedral angle was performed first to find an intermediate geometry. Subsequently, the isomerization pathway was explored via individual steps using a series of mode redundant geometry optimizations (internal coordinates potential energy surface scans) and geometry relaxations leading to the s structure. The prominent geometries (intermediates) of the isomerization pathway are chosen and compared to the a and s structures, and geometry relaxations of the protonated forms of selected intermediates are considered.
研究了含有两个通过碳碳(C-C)σ键连接的 15 元八氮杂环单元的镍(II)二聚体的去质子化形式的反(a)到合(s)异构化途径。对于最初的反 (a) 结构,建议对其中一个桥接(sp3 杂化)碳原子进行去质子化处理,以实现从 a 到 s 的几何扭曲。首先围绕桥接 C-C 二面角进行 360° 扫描,以找到中间几何结构。随后,通过一系列模式冗余几何优化(内部坐标势能面扫描)和几何松弛,探索了通向 s 结构的单步异构化途径。我们选择了异构化途径中的主要几何结构(中间体),并将其与 a 和 s 结构进行了比较,还考虑了所选中间体质子化形式的几何松弛。
{"title":"Isomerization pathway of a C–C sigma bond in a bis(octaazamacrocycle)dinickel(II) complex activated by deprotonation: a DFT study","authors":"Ingrid Jelemenska, Michal Zalibera, Peter Rapta, Anatoly A. Dobrov, Vladimir B. Arion, Lukas Bucinsky","doi":"10.1007/s00214-024-03100-5","DOIUrl":"https://doi.org/10.1007/s00214-024-03100-5","url":null,"abstract":"<p>The anti (<b>a</b>) to syn (<b>s</b>) isomerization pathway of the deprotonated form of the dimer with two nickel(II) 15-membered octaazamacrocyclic units connected via a carbon–carbon (C–C) σ bond was investigated. For the initial anti (<b>a</b>) structure, a deprotonation of one of the bridging (<i>sp</i><sup>3</sup> hybridized) carbon atoms is suggested to allow for an <b>a</b> to <b>s</b> geometry twist. A 360° scan around the bridging C–C dihedral angle was performed first to find an intermediate geometry. Subsequently, the isomerization pathway was explored via individual steps using a series of mode redundant geometry optimizations (internal coordinates potential energy surface scans) and geometry relaxations leading to the <b>s</b> structure. The prominent geometries (intermediates) of the isomerization pathway are chosen and compared to the <b>a</b> and <b>s</b> structures, and geometry relaxations of the protonated forms of selected intermediates are considered.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140125085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-13DOI: 10.1007/s00214-024-03097-x
Ali Abdulhasan Rasool Al-Karaawi, Muhsen Abood Muhsen Al-Ibadi
The tri-nuclear heterometallic tetrahedral cluster [Mo–Ru–Co(µ3–S)(CO)8(Cp)COOCH3] (Cp = η5-C5H4) was studied employing quantum theory of atoms in molecules (QTAIM) to examine bonding interactions, including metal–metal (M–M), metal–sulfur (M–S), metal–carbonyl (M–CO), and metal–cyclopentadienyl (M–Cp) interactions. The electron density of bonding interactions within the cluster has its topological properties calculated based on this theory. Interestingly, the computed local topological characteristics for the Mo–Ru bond show notable distinctions in comparison to the parameters for interactions involving Mo–Co and Ru–Co, since for the latter, critical points and paths were not observed. The distribution of electron density was notably affected by the presence of bridging sulfide ligands in Mo…Co, Ru…Co interactions, much more than in the Mo–Ru bond. The characteristics of the latter bond exhibited attributes typical of interactions between open-shell metals. These features included slightly positive values for ρ(b) and ∇2ρ(b), along with small negative values of H(b)/ρ(b) approaching zero. Additionally, using the source function (SF) and electron localization function (ELF) methods, more focus has been given to the Mo–Ru bond. The core part, [Mo–Ru–Co(µ3–S)], was found to have a multicenter 4c–6e interaction. In this core, the three M–S bonds between the metal atoms and the sulfide ligand showed similar topological parameters that were typical of open-shell (covalent) interactions. Substantial π–back donation from CO to M was identified through the execution of δ(M…OCO) delocalization index calculations.
{"title":"A topological analysis of the bonding interaction within the tri-nuclear heterometallic cluster [Mo–Ru–Co(µ3–S)(CO)8(Cp)COOCH3], (Cp = η5-C5H4)","authors":"Ali Abdulhasan Rasool Al-Karaawi, Muhsen Abood Muhsen Al-Ibadi","doi":"10.1007/s00214-024-03097-x","DOIUrl":"https://doi.org/10.1007/s00214-024-03097-x","url":null,"abstract":"<p>The tri-nuclear heterometallic tetrahedral cluster [Mo–Ru–Co(<i>µ</i><sub>3</sub>–S)(CO)<sub>8</sub>(Cp)COOCH<sub>3</sub>] (Cp = <i>η</i><sup>5</sup>-C<sub>5</sub>H<sub>4</sub>) was studied employing quantum theory of atoms in molecules (QTAIM) to examine bonding interactions, including metal–metal (M–M), metal–sulfur (M–S), metal–carbonyl (M–CO), and metal–cyclopentadienyl (M–Cp) interactions. The electron density of bonding interactions within the cluster has its topological properties calculated based on this theory. Interestingly, the computed local topological characteristics for the Mo–Ru bond show notable distinctions in comparison to the parameters for interactions involving Mo–Co and Ru–Co, since for the latter, critical points and paths were not observed. The distribution of electron density was notably affected by the presence of bridging sulfide ligands in Mo…Co, Ru…Co interactions, much more than in the Mo–Ru bond. The characteristics of the latter bond exhibited attributes typical of interactions between open-shell metals. These features included slightly positive values for <i>ρ</i><sub><i>(</i>b)</sub> and ∇<sup>2</sup><i>ρ</i><sub>(b)</sub>, along with small negative values of <i>H</i><sub>(b)</sub>/<i>ρ</i><sub>(b)</sub> approaching zero. Additionally, using the source function (SF) and electron localization function (ELF) methods, more focus has been given to the Mo–Ru bond. The core part, [Mo–Ru–Co(<i>µ</i><sub>3</sub>–S)], was found to have a multicenter 4<i>c</i>–6<i>e</i> interaction. In this core, the three M–S bonds between the metal atoms and the sulfide ligand showed similar topological parameters that were typical of open-shell (covalent) interactions. Substantial <i>π</i>–back donation from CO to M was identified through the execution of <i>δ</i>(M…O<sub>CO</sub>) delocalization index calculations.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140129899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-05DOI: 10.1007/s00214-024-03095-z
Abstract
In the realm of studying supramolecular polymers using computer simulations, the task of generating appropriate initial structures poses a significant challenge, primarily owing to the extensive range of potential configurations. In this study, we introduce StackGen, an open-source framework designed to efficiently create energy-optimized one-dimensional supramolecular polymer structures with minimal computational overhead. This tool utilizes the particle swarm optimization (PSO) algorithm in conjunction with a semiempirical quantum mechanical approach to identify low-energy supramolecular stack configurations from a diverse set of possibilities. These configurations result from the translational and rotational adjustments of adjacent molecules around monomers along various axes. The tool also considers various structural factors, including the presence of functional side groups and the extent of intermolecular (pi)–(pi) stacking interactions. Extensive testing across different molecules demonstrates StackGen’s ability to produce low-energy structures with negligible computational costs. Additionally, the tool incorporates features for optimizing PSO hyperparameters in real-time, thus improving convergence. The tool provides a convenient means of generating structures suitable for both molecular simulations and quantum mechanical calculations.
{"title":"Constructing one-dimensional supramolecular polymer structures using particle swarm optimization technique","authors":"","doi":"10.1007/s00214-024-03095-z","DOIUrl":"https://doi.org/10.1007/s00214-024-03095-z","url":null,"abstract":"<h3>Abstract</h3> <p>In the realm of studying supramolecular polymers using computer simulations, the task of generating appropriate initial structures poses a significant challenge, primarily owing to the extensive range of potential configurations. In this study, we introduce <em>StackGen</em>, an open-source framework designed to efficiently create energy-optimized one-dimensional supramolecular polymer structures with minimal computational overhead. This tool utilizes the particle swarm optimization (PSO) algorithm in conjunction with a semiempirical quantum mechanical approach to identify low-energy supramolecular stack configurations from a diverse set of possibilities. These configurations result from the translational and rotational adjustments of adjacent molecules around monomers along various axes. The tool also considers various structural factors, including the presence of functional side groups and the extent of intermolecular <span> <span>(pi)</span> </span>–<span> <span>(pi)</span> </span> stacking interactions. Extensive testing across different molecules demonstrates <em>StackGen</em>’s ability to produce low-energy structures with negligible computational costs. Additionally, the tool incorporates features for optimizing PSO hyperparameters in real-time, thus improving convergence. The tool provides a convenient means of generating structures suitable for both molecular simulations and quantum mechanical calculations.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140033849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-01DOI: 10.1007/s00214-024-03099-9
Amrutha Kizhuvedath, Jose John Mallikasseri, Jomon Mathew
Cyclotrisilenes can pursue four types of reaction pathways with unsaturated substrates: π-addition, σ-insertion, exocyclic σ-insertion, and ring-opening reactions. A computational investigation of all these reaction pathways of 1,2,3,3-tetramethyl cyclotrisilene c-Si3Me4 (I) and 1,2-bis(trimethylsilyl)-3,3-dimethyl cyclotrisilene c-Si3Me2(SiMe3)2 (II) with phenylacetylene (R1) and benzaldehyde (R2) is carried out. The reaction pathways are found to be significantly influenced by the substituents attached to the cyclotrisilene ring. Both the π-addition and the σ-insertion reactions proceed with moderate activation energy and high exoergicity, and the electronic nature of the functional group is crucial in deciding the favorable pathway. The exocyclic σ-insertion reactions are found to possess a huge energy barrier, irrespective of the steric and electronic nature of cyclotrisilenes and the substrates. While the course of the reaction and the viability of the ring-opening reaction with phenylacetylene are impacted by the nature of cyclotrisilene, the ring-opening reactions of I and II with benzaldehyde are both highly endoergic.
环三苯乙烯可以与不饱和底物进行四种类型的反应途径:π-加成、σ-插入、外环σ-插入和开环反应。对 1,2,3,3-四甲基环三硅烯 c-Si3Me4 (I) 和 1,2-双(三甲基硅基)-3,3-二甲基环三硅烯 c-Si3Me2(SiMe3)2 (II) 与苯乙炔 (R1) 和苯甲醛 (R2) 的所有这些反应途径进行了计算研究。研究发现,环三苯乙烯环上的取代基对反应途径有很大影响。π-加成反应和σ-插入反应都以中等活化能和较高的外能进行,而官能团的电子性质是决定有利反应途径的关键。研究发现,无论环三苯乙烯和底物的立体和电子性质如何,外环σ插入反应都具有巨大的能障。虽然与苯乙炔的开环反应的过程和可行性受到环三苯乙烯性质的影响,但 I 和 II 与苯甲醛的开环反应都具有很高的内能。
{"title":"Unraveling the reaction pathways of cyclotrisilenes: a computational analysis","authors":"Amrutha Kizhuvedath, Jose John Mallikasseri, Jomon Mathew","doi":"10.1007/s00214-024-03099-9","DOIUrl":"https://doi.org/10.1007/s00214-024-03099-9","url":null,"abstract":"<p>Cyclotrisilenes can pursue four types of reaction pathways with unsaturated substrates: <i>π</i>-addition, <i>σ</i>-insertion, exocyclic <i>σ</i>-insertion, and ring-opening reactions. A computational investigation of all these reaction pathways of 1,2,3,3-tetramethyl cyclotrisilene c-Si<sub>3</sub>Me<sub>4</sub> (<b>I</b>) and 1,2-bis(trimethylsilyl)-3,3-dimethyl cyclotrisilene c-Si<sub>3</sub>Me<sub>2</sub>(SiMe<sub>3</sub>)<sub>2</sub> (<b>II</b>) with phenylacetylene (<b>R1</b>) and benzaldehyde (<b>R2</b>) is carried out. The reaction pathways are found to be significantly influenced by the substituents attached to the cyclotrisilene ring. Both the <i>π</i>-addition and the <i>σ</i>-insertion reactions proceed with moderate activation energy and high exoergicity, and the electronic nature of the functional group is crucial in deciding the favorable pathway. The exocyclic <i>σ</i>-insertion reactions are found to possess a huge energy barrier, irrespective of the steric and electronic nature of cyclotrisilenes and the substrates. While the course of the reaction and the viability of the ring-opening reaction with phenylacetylene are impacted by the nature of cyclotrisilene, the ring-opening reactions of <b>I</b> and <b>II</b> with benzaldehyde are both highly endoergic.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140016688","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
NH3 is the most basic raw material in industrial and agricultural production, and it is also an excellent hydrogen carrier. The high energy consumption and pollution of traditional NH3 synthesis methods limit their further development. As an environmentally friendly and efficient industrial technology, electrocatalysis has important application value in the field of green energy storage and conversion. Therefore, the development of electrocatalysts with high activity, good stability and low cost is the key to improve the efficiency of the nitrogen reduction reaction (NRR) to generate NH3. Herein, a series of transition metal clusters loaded onto the di-vacancy graphene (XmYn@Gra(X, Y = Fe, Co and Ni; m + n = 3)) as electrocatalysts were designed. By calculating the free energy of the first and last hydrogenation steps, it was found that NiCo2@Gra and FeCo2@Gra had the best catalytic activity. The first hydrogenation process from *N2 to *N2H was potential-determining step, and the corresponding limiting potentials were − 0.57 and − 0.51 V, respectively. In addition, the reasons for the high catalytic activity of NiCo2@Gra and FeCo2@Gra were further elucidated by analyzing the electronic properties. This study provides a new strategy for the use of cluster catalysts in NRR process and a new idea for the fixation and conversion of N2.
NH3 是工农业生产中最基本的原料,也是一种优良的氢载体。传统的 NH3 合成方法能耗高、污染大,限制了其进一步发展。电催化技术作为一种环保高效的工业技术,在绿色能源储存和转化领域具有重要的应用价值。因此,开发活性高、稳定性好、成本低的电催化剂是提高氮还原反应生成 NH3 效率的关键。本文设计了一系列负载在二空位石墨烯上的过渡金属团簇(XmYn@Gra(X, Y = Fe, Co and Ni; m + n = 3))作为电催化剂。通过计算第一个和最后一个氢化步骤的自由能,发现 NiCo2@Gra 和 FeCo2@Gra 的催化活性最好。从 *N2 到 *N2H 的第一个氢化过程是电位决定步骤,相应的极限电位分别为 - 0.57 和 - 0.51 V。此外,通过分析电子特性,进一步阐明了 NiCo2@Gra 和 FeCo2@Gra 具有高催化活性的原因。该研究为在氮还原反应过程中使用团簇催化剂提供了新策略,也为固定和转化 N2 提供了新思路。
{"title":"The graphene-supported transition metal cluster as efficient electrocatalyst for nitrogen reduction reaction","authors":"Jinqiang Li, Jiale Liu, Hui Li, Chaozheng He, Yong Wei, Huijun Kong, Wei Song","doi":"10.1007/s00214-024-03101-4","DOIUrl":"https://doi.org/10.1007/s00214-024-03101-4","url":null,"abstract":"<p>NH<sub>3</sub> is the most basic raw material in industrial and agricultural production, and it is also an excellent hydrogen carrier. The high energy consumption and pollution of traditional NH<sub>3</sub> synthesis methods limit their further development. As an environmentally friendly and efficient industrial technology, electrocatalysis has important application value in the field of green energy storage and conversion. Therefore, the development of electrocatalysts with high activity, good stability and low cost is the key to improve the efficiency of the nitrogen reduction reaction (NRR) to generate NH<sub>3</sub>. Herein, a series of transition metal clusters loaded onto the di-vacancy graphene (<i>X</i><sub><i>m</i></sub><i>Y</i><sub><i>n</i></sub>@Gra(<i>X</i>, <i>Y</i> = Fe, Co and Ni; <i>m</i> + <i>n</i> = 3)) as electrocatalysts were designed. By calculating the free energy of the first and last hydrogenation steps, it was found that NiCo<sub>2</sub>@Gra and FeCo<sub>2</sub>@Gra had the best catalytic activity. The first hydrogenation process from *N<sub>2</sub> to *N<sub>2</sub>H was potential-determining step, and the corresponding limiting potentials were − 0.57 and − 0.51 V, respectively. In addition, the reasons for the high catalytic activity of NiCo<sub>2</sub>@Gra and FeCo<sub>2</sub>@Gra were further elucidated by analyzing the electronic properties. This study provides a new strategy for the use of cluster catalysts in NRR process and a new idea for the fixation and conversion of N<sub>2</sub>.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140007983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-24DOI: 10.1007/s00214-024-03094-0
Anindita Pati, T. K. Kundu, Snehanshu Pal
This study focuses on conducting a comparative study of the extraction capacities of alizarin-oxalate (AR-Ox) ligands with La3+ and Nd3+ in acidic, neutral, and alkaline mediums. Density functional theory calculations at ωB97X-D/6-311++G(d,p)/SDD level have been performed for structural, thermochemical, frontier-orbital (highest occupied molecular orbitals and lowest unoccupied molecular orbitals), natural bond orbital, reduced density gradient (RDG), and density of state analysis for alizarin-oxalate-La(III) (AR-Ox-La) and alizarin-oxalate-Nd(III) (AR-Ox-Nd) complexes. The bonding characteristics of La3+ & Nd3+ ions with alizarin-oxalate ligand have been analysed using the quantum theory of atoms in molecules, revealing the presence of an intermediate type of bond between closed-shell and shared-shell electrons in (La/Nd)-O, (La/Nd)-C. The reduced density gradient (RDG) and iso-surface generated through the Multiwfn program shows mostly hydrogen-like and van der Waals interaction between La3+/Nd3+ and oxygen atoms of alizarin-oxalate ligand except for some of the complexes showing the presence of non-bonded/repulsive (La/Nd)-O interaction. Thermochemical, DOS, and natural bond orbital analysis reveals alizarin-oxalate-(La3+/Nd3+) complexes in the alkaline medium is more stable than in neutral and acidic medium, and the stability of AR-Ox-Nd complexes is more than AR-Ox-La complexes. It is observed that participation of oxygen atoms from both alizarin and oxalate in bond formation with lanthanides enhances the stability of alizarin-oxalate-lanthanide complexes, emphasizing the pivotal role of ligand coordination modes. This work illustrates the subtle differences in chelating properties of alizarin-oxalate ligands with La3+ and Nd3+ for designing new ligands for efficient selective lanthanide separation.
{"title":"Chelating effect of alizarin-oxalate on La3+ and Nd3+ in acidic, basic and neutral medium: a DFT study","authors":"Anindita Pati, T. K. Kundu, Snehanshu Pal","doi":"10.1007/s00214-024-03094-0","DOIUrl":"https://doi.org/10.1007/s00214-024-03094-0","url":null,"abstract":"<p>This study focuses on conducting a comparative study of the extraction capacities of alizarin-oxalate (AR-Ox) ligands with La<sup>3+</sup> and Nd<sup>3+</sup> in acidic, neutral, and alkaline mediums. Density functional theory calculations at ωB97X-D/6-311++G(d,p)/SDD level have been performed for structural, thermochemical, frontier-orbital (highest occupied molecular orbitals and lowest unoccupied molecular orbitals), natural bond orbital, reduced density gradient (RDG), and density of state analysis for alizarin-oxalate-La(III) (AR-Ox-La) and alizarin-oxalate-Nd(III) (AR-Ox-Nd) complexes. The bonding characteristics of La<sup>3+</sup> & Nd<sup>3+</sup> ions with alizarin-oxalate ligand have been analysed using the quantum theory of atoms in molecules, revealing the presence of an intermediate type of bond between closed-shell and shared-shell electrons in (La/Nd)-O, (La/Nd)-C. The reduced density gradient (RDG) and iso-surface generated through the Multiwfn program shows mostly hydrogen-like and van der Waals interaction between La<sup>3+</sup>/Nd<sup>3+</sup> and oxygen atoms of alizarin-oxalate ligand except for some of the complexes showing the presence of non-bonded/repulsive (La/Nd)-O interaction. Thermochemical, DOS, and natural bond orbital analysis reveals alizarin-oxalate-(La<sup>3+</sup>/Nd<sup>3+</sup>) complexes in the alkaline medium is more stable than in neutral and acidic medium, and the stability of AR-Ox-Nd complexes is more than AR-Ox-La complexes. It is observed that participation of oxygen atoms from both alizarin and oxalate in bond formation with lanthanides enhances the stability of alizarin-oxalate-lanthanide complexes, emphasizing the pivotal role of ligand coordination modes. This work illustrates the subtle differences in chelating properties of alizarin-oxalate ligands with La<sup>3+</sup> and Nd<sup>3+</sup> for designing new ligands for efficient selective lanthanide separation.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139953318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-21DOI: 10.1007/s00214-024-03096-y
Lin Zhang, Hongshan Chen
The atomic-scale structures of Al–Si eutectics and hypereutectic are studied by using global structure searching method combined with ab initio density functional theories. The chemical components Al7Si, Al6Si and Al4Si, with silicon contents of 12.9, 14.7 and 20.6 wt%, are set for searching the lowest-energy structures. The global search results show that all of the low-energy structures demonstrate the fcc structure feature of pure aluminum crystal; while, the alloy structures distort slightly due to the addition of silicon. In the term of binding energy, the stabilities of the alloys enhance with increasing the silicon contents. The binding energies are approximated as the sum of the bond energies, and the least square fitting results give the Al–Al, Al–Si and Si–Si bond energies as − 0.624, − 0.731 and − 0.819 eV, respectively. Forming two Al–Si bonds sacrifices one Si–Si and one Al–Al bonds, and the Al–Si alloys have an energy gain of − 0.019 eV. It suggests that dispersion of silicon atoms in the alloys is favorable for the stability. The mechanical properties of the structures are calculated. While the bulk moduli of the alloys are very close, the shear and Young’s moduli are quite different for different structures with different distributions of silicon atoms.
{"title":"The global low-energy structures of Al–Si eutectic and hypereutectic","authors":"Lin Zhang, Hongshan Chen","doi":"10.1007/s00214-024-03096-y","DOIUrl":"https://doi.org/10.1007/s00214-024-03096-y","url":null,"abstract":"<p>The atomic-scale structures of Al–Si eutectics and hypereutectic are studied by using global structure searching method combined with ab initio density functional theories. The chemical components Al<sub>7</sub>Si, Al<sub>6</sub>Si and Al<sub>4</sub>Si, with silicon contents of 12.9, 14.7 and 20.6 wt%, are set for searching the lowest-energy structures. The global search results show that all of the low-energy structures demonstrate the fcc structure feature of pure aluminum crystal; while, the alloy structures distort slightly due to the addition of silicon. In the term of binding energy, the stabilities of the alloys enhance with increasing the silicon contents. The binding energies are approximated as the sum of the bond energies, and the least square fitting results give the Al–Al, Al–Si and Si–Si bond energies as − 0.624, − 0.731 and − 0.819 eV, respectively. Forming two Al–Si bonds sacrifices one Si–Si and one Al–Al bonds, and the Al–Si alloys have an energy gain of − 0.019 eV. It suggests that dispersion of silicon atoms in the alloys is favorable for the stability. The mechanical properties of the structures are calculated. While the bulk moduli of the alloys are very close, the shear and Young’s moduli are quite different for different structures with different distributions of silicon atoms.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139923541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-12DOI: 10.1007/s00214-024-03091-3
Abstract
We performed several types of ab initio calculations, from Hartree-Fock to Complete-Active-Space second-order perturbation theory and Coupled Cluster, on compact clusters of stoichiometry X(_4)Y(_4), where X and Y are atoms belonging to the second row of the periodic table. More precisely, we considered the “cubic” structures of three isoelectronic groups, having a total of 48, 52, and 56-electrons, respectively. Notice that the highly symmetric cubic clusters of type X(_8) are characterized by an (O_h) symmetry group, while the X(_4)Y(_4) structures, with X(ne)Y, have at most a (T_d) symmetry. Binding energies and wave function analysis of these clusters have been performed, in order to investigate the nature, and the electron delocalization of these systems and establish a comparison between them. To this purpose, we also computed the Total-Position Spread tensor for each structure, a quantity which is related to the multi-reference nature of a system wave function.
摘要 我们对原子序数为 X (_4) Y (_4) 的紧凑簇进行了几种类型的原子序数计算,从哈特里-福克到完全活动空间二阶扰动理论和耦合簇,其中 X 和 Y 是属于元素周期表第二行的原子。更确切地说,我们考虑了三个等电子群的 "立方 "结构,它们分别拥有 48、52 和 56 个电子。请注意,X (_8)型的高度对称立方团簇具有 (O_h) 对称团的特征,而 X (_4)Y (_4)结构中的 X (ne)Y 最多具有 (T_d) 对称性。我们对这些团簇进行了结合能和波函数分析,以研究这些体系的性质和电子析出,并建立它们之间的比较。为此,我们还计算了每种结构的总位置展宽张量(Total-Position Spread tensor),这个量与系统波函数的多参考性质有关。
{"title":"Three isoelectronic families of X $$_4$$ Y $$_4$$ cubic systems","authors":"","doi":"10.1007/s00214-024-03091-3","DOIUrl":"https://doi.org/10.1007/s00214-024-03091-3","url":null,"abstract":"<h3>Abstract</h3> <p>We performed several types of <em>ab initio </em> calculations, from Hartree-Fock to Complete-Active-Space second-order perturbation theory and Coupled Cluster, on compact clusters of stoichiometry X<span> <span>(_4)</span> </span>Y<span> <span>(_4)</span> </span>, where X and Y are atoms belonging to the second row of the periodic table. More precisely, we considered the “cubic” structures of three isoelectronic groups, having a total of 48, 52, and 56-electrons, respectively. Notice that the highly symmetric cubic clusters of type X<span> <span>(_8)</span> </span> are characterized by an <span> <span>(O_h)</span> </span> symmetry group, while the X<span> <span>(_4)</span> </span>Y<span> <span>(_4)</span> </span> structures, with X<span> <span>(ne)</span> </span>Y, have at most a <span> <span>(T_d)</span> </span> symmetry. Binding energies and wave function analysis of these clusters have been performed, in order to investigate the nature, and the electron delocalization of these systems and establish a comparison between them. To this purpose, we also computed the Total-Position Spread tensor for each structure, a quantity which is related to the multi-reference nature of a system wave function.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139759819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study focuses on investigating the spring properties of helicenes through DFT theoretical calculations. The energy change during stretching was observed by incrementally scanning the distance between both ends of the helicene from its stable state. The stiffness (k value) of each helicene was also determined at different stretching states. Interestingly, the k value was found to be non-constant during stretching, suggesting that helicenes do not behave as ideal springs. Furthermore, the effects of heteroatom doping and lateral π-extension on [6]helicene were examined, indicating that these factors have minimal impact on the spring nature of helicenes. Additionally, the study extended to longer helicenes, namely [12] and [18]helicenes. It was observed that the stiffness at the middle part of the helicene is greater than at the terminal parts, and the helical structures begin to collapse when the stretching length reaches approximately 2.5 times the stable state. We expected this work could bring innovative concept in future design of molecular devices.
{"title":"A DFT study on spring property of helicenes","authors":"Xunshan Liu, Xingyuan Cui, Xu Zhang, Jian-Ping Wu, Chengshuo Shen","doi":"10.1007/s00214-024-03093-1","DOIUrl":"https://doi.org/10.1007/s00214-024-03093-1","url":null,"abstract":"<p>This study focuses on investigating the spring properties of helicenes through DFT theoretical calculations. The energy change during stretching was observed by incrementally scanning the distance between both ends of the helicene from its stable state. The stiffness (<i>k</i> value) of each helicene was also determined at different stretching states. Interestingly, the <i>k</i> value was found to be non-constant during stretching, suggesting that helicenes do not behave as ideal springs. Furthermore, the effects of heteroatom doping and lateral <i>π</i>-extension on [6]helicene were examined, indicating that these factors have minimal impact on the spring nature of helicenes. Additionally, the study extended to longer helicenes, namely [12] and [18]helicenes. It was observed that the stiffness at the middle part of the helicene is greater than at the terminal parts, and the helical structures begin to collapse when the stretching length reaches approximately 2.5 times the stable state. We expected this work could bring innovative concept in future design of molecular devices.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139759714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}