Theoretical Chemistry Accounts最新文献_第3页

A theoretical study of the comparison of gas-phase electronic properties and structure of pyridinium-based ionic liquids with different anions (chloride, bromide and iodide) 关于含有不同阴离子（氯化物、溴化物和碘化物）的吡啶基离子液体的气相电子特性和结构比较的理论研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-05-04 DOI: 10.1007/s00214-024-03118-9

Zahra Fakhri, Azim Soltanabadi, Samaneh Kiani, Afsaneh Maleki

{"title":"A theoretical study of the comparison of gas-phase electronic properties and structure of pyridinium-based ionic liquids with different anions (chloride, bromide and iodide)","authors":"Zahra Fakhri, Azim Soltanabadi, Samaneh Kiani, Afsaneh Maleki","doi":"10.1007/s00214-024-03118-9","DOIUrl":"https://doi.org/10.1007/s00214-024-03118-9","url":null,"abstract":"Structures of pyridinium-based ionic liquids containing 1-methylpyridinium [MP]+, 1-ethylpyridinium [EP]+ and 1-propylpyridinium [PP]+ with halide anions (X) where X = Cl−, Br− and I− were studied using density functional theory and the most stable structures of these ionic liquids were compared. Then electronic and structural properties were extracted for the desired liquids. The results show that in the most stable conformers, in these ILs, Cl− and Br− anions prefer to be placed almost in the plane of the pyridinium ring, while I− prefers the position almost vertical to the plane of the pyridinium ring. In order to investigate the hydrogen bonds between molecules by atoms in molecules (AIMs) and natural bonding orbital (NBO) were studied. The calculated thermodynamic functions show that the interaction of the cation–anion pair in ionic liquids containing Cl− and Br− anions is greater than I−, and these interactions decrease with the increase in the atomic weight of the halide. Molecular orbital theory has also been used to calculate quantities related to their stability and activity. Also, ionic liquids containing iodine anion have a high dipole moment compared to ionic liquids containing chloride and bromide. The results of this study show that the properties of Any ILs can be controlled by choosing the appropriate anions.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"25 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140933865","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}

引用次数: 0

Investigation of solvent effects on the aromaticity of hydroxybenzenes, considering magnetically induced current densities in adducts with explicit water molecules 研究溶剂对羟苯芳香性的影响，考虑与明确水分子加合物中的磁感应电流密度

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-28 DOI: 10.1007/s00214-024-03116-x

Liliana Mammino, Luis Alvarez-Thon

{"title":"Investigation of solvent effects on the aromaticity of hydroxybenzenes, considering magnetically induced current densities in adducts with explicit water molecules","authors":"Liliana Mammino, Luis Alvarez-Thon","doi":"10.1007/s00214-024-03116-x","DOIUrl":"https://doi.org/10.1007/s00214-024-03116-x","url":null,"abstract":"Evaluating the effects of a solvent on the properties of a solute molecule is important to understand its behavior in a solution of that solvent; this, in turn, is important because most reactions—including all the reactions in biological systems—occur in solution. In its most common definition, aromaticity is a property of molecules with delocalized electrons in a ring. It significantly influences their behavior and, therefore, it is important to evaluate the effects of a solvent on it. The most powerful magnetic criterion to estimate aromaticity considers magnetically induced current densities in the ring. The present work applies this approach to adducts of hydroxybenzenes with explicit water molecules. Hydroxybenzenes are selected as the simplest aromatic systems capable of forming solute–solvent hydrogen bonds with water molecules. Hydroxybenzenes without consecutive OH groups are selected to avoid the influence of intramolecular hydrogen bonds between OHs. Current densities are calculated focusing on the aromatic rings, and the effect of the solvent is highlighted by the density changes caused by the presence of the water molecules attached to the hydroxybenzene molecule. The results show that the strength of the ring current decreases as the number of OH groups in the molecule increases. The strength does not change greatly in the adducts with respect to the isolated molecules: the change extent and direction depend mostly on the arrangement of water molecules around the central molecule. The current density maps show that the water molecules may also be involved in the current flow.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"5 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140811847","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}

引用次数: 0

Silatranes and germatranes as the systems with intramolecular tetrel bonds 硅烷和锗烷是具有分子内四键的体系

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-16 DOI: 10.1007/s00214-024-03112-1

Ekaterina V. Bartashevich, Roman L. Regel, Vladimir G. Tsirelson

{"title":"Silatranes and germatranes as the systems with intramolecular tetrel bonds","authors":"Ekaterina V. Bartashevich, Roman L. Regel, Vladimir G. Tsirelson","doi":"10.1007/s00214-024-03112-1","DOIUrl":"https://doi.org/10.1007/s00214-024-03112-1","url":null,"abstract":"We studied intramolecular noncovalent bonds in organogermanium or organosilicon cyclic esters of tris(2-hydroxyalkyl)amines called silatranes and germatranes. We have shown that the N…Si and N…Ge interactions, well known as hypervalent or transannular bonds, can be rightfully categorized as the strong tetrel bonds (TtB). In the wide set of silatranes and germatranes, the TtB strength is under the influence of the Y substituent at Tt atom in the N…Tt–Y fragment and the features of crystalline environment. We have disclosed the quantitative trends in electronic features of N…Tt tetrel bonds and demonstrated the applicability of criteria based on the positions of extremes in electron density and electrostatic potential along the line between N and Tt atoms to compare the strength of the N…Si and N…Ge tetrel bonds. An important observation is that the dependence of gap width on bond lengths is not linear for silatranes. In order to solve this problem we have analyzed the features of total static potential. The gap between positions of extremes in electrostatic and total static potentials is wide for the weak tetrel bonds and narrow for the strong ones.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"39 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601452","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}

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Quenching of reactive species by Avenanthramides: theoretical insight to the thermodynamics of electron transfer 文竹酰胺对活性物种的淬灭：电子转移热力学的理论启示

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-13 DOI: 10.1007/s00214-024-03111-2

P. C. Sumayya, K. Muraleedharan

{"title":"Quenching of reactive species by Avenanthramides: theoretical insight to the thermodynamics of electron transfer","authors":"P. C. Sumayya, K. Muraleedharan","doi":"10.1007/s00214-024-03111-2","DOIUrl":"https://doi.org/10.1007/s00214-024-03111-2","url":null,"abstract":"Avenanthramides (AVs) are the phytochemicals found in cereals exclusively in oats. These are widely known natural substances that have antioxidant properties. The free radical deactivation potential of the eight AVs against five reactive species has been studied in physiological pH. At physiological pH, the radical quenching processes were studied using the sequential proton loss followed by electron transfer (SPLET) from the phenolic hydroxyl groups. Using density functional theory (DFT) computations, theoretical studies have been carried out in the gas phase and aqueous solution at M06-2X/6-31 + G (d,p) level of theory. The free radical scavenging ability of the studied AVs was analyzed by using conceptual density functional theory-based parameters and electrostatic potential analysis. By examining the hydrogen atom and electron affinities of each reactive species, the relative destructive potential of each has been compared. The electron transfer capabilities between the studied compound and reactive species were identified by utilizing the ionization energy and electron affinity plots. Additionally, by calculating the redox potentials and equilibrium constants for the entire process in the aqueous solution, the viability of scavenging the free radical species by selected AVs (both in neutral and mono-deprotonated) has been investigated. From the analysis, the neutral as well as the mono-deprotonated form of AVs are found to scavenge •OH and •OOH, and •NO2 radicals effectively, while they are inefficacious toward the O2•‾ and •NO radicals.<h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"10 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601450","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}

引用次数: 0

First-principles calculations on the structures and electronic properties of the TMW2On (TM = Mn–Ni, n = 1–6) clusters 关于 TMW2On（TM = 锰-镍，n = 1-6）团簇结构和电子特性的第一性原理计算

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-12 DOI: 10.1007/s00214-024-03113-0

Zhi Li, Zi-hao Wu, Zhen Zhao

{"title":"First-principles calculations on the structures and electronic properties of the TMW2On (TM = Mn–Ni, n = 1–6) clusters","authors":"Zhi Li, Zi-hao Wu, Zhen Zhao","doi":"10.1007/s00214-024-03113-0","DOIUrl":"https://doi.org/10.1007/s00214-024-03113-0","url":null,"abstract":"Transition metals can enhance the electronic attributes of tungsten oxides. In this study, we focused on W2On (n = 1–6) clusters as a representative examples of tungsten oxide clusters with varying oxygen concentrations. The structures and electronic properties of the TMWOn (TM = Mn–Ni) clusters have been calculated using first-principles. The ground-state TMWOn clusters share some structural similarities with the ground-state W2On (n = 1–6) clusters. The W–O bonds of the TMWO2 (TM = Fe–Ni) clusters are significantly distorted into a triangular structure. The NiWOn (n = 1–2) and CoWOn (n = 3–5) clusters display greater thermodynamic stability than other TMWOn clusters. Among the TMWOn clusters, the W2O4, W2O6, MnWO, MnWO3, MnWO6, FeWO, FeWO4, FeWO6, CoWO, CoWO6, NiWO2, NiWO5 clusters are more kinetically stable. Furthermore, the amount of charge transfer between the TM atoms and W2On clusters increases from 0.050 |e| to 1.066 |e| as the number of oxygen atoms increases. The 4s orbital electrons of the TM atoms for the TMWOn clusters are partially transferred to the neighboring O atoms.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"37 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601584","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}

引用次数: 0

Reaction of [2-(3-hetaryl-1,2,4-triazol-5-yl)phenyl]amines with ketones: a density functional theory study 2-(3-乙酰基-1,2,4-三唑-5-基)苯基]胺与酮的反应：密度泛函理论研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-04-04 DOI: 10.1007/s00214-024-03110-3

Olena O. Pylypenko, Liudmyla K. Sviatenko, Kostyantin P. Shabelnyk, Sergiy I. Kovalenko, Sergiy I. Okovytyy

{"title":"Reaction of [2-(3-hetaryl-1,2,4-triazol-5-yl)phenyl]amines with ketones: a density functional theory study","authors":"Olena O. Pylypenko, Liudmyla K. Sviatenko, Kostyantin P. Shabelnyk, Sergiy I. Kovalenko, Sergiy I. Okovytyy","doi":"10.1007/s00214-024-03110-3","DOIUrl":"https://doi.org/10.1007/s00214-024-03110-3","url":null,"abstract":"The derivatives of 1,2,4- triazole have attracted great attention among medicinal chemists due to their wide range of biological activity, good pharmacodynamic and pharmacokinetic profiles, and low toxicity, that necessitates the development of various synthesis methods and a comprehensive study of their reaction mechanisms. A detailed investigation of possible pathways for formation of new spiro-condensed [1,2,4]triazolo[1,5-c]quinazolines, that combine two structural domains with different biological properties, was performed by computational study at the SMD/B3lyp/6-31+G(d) theory level. The mechanism of interaction between [2-(3-hetaryl-1,2,4-triazol-5-yl)phenyl]amine and cyclohexanone in methanol involves three main processes: formation of carbinolamine by addition of an amine to double bond C=O, elimination of a water molecule, and intramolecular cyclization leading to formation of spiro compounds. Results show increase in reactivity of reactants during acid-catalyzed reaction compared to uncatalyzed one. The nature of the heterocyclic substituent on the triazole ring has little effect on the reaction energy, while the mechanism is unchanged.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"55 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140601457","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}

引用次数: 0

Theoretical investigation on phosphorescent platinum complexes based on two tetradentate bipyridine ligands 基于两个四价联吡啶配体的磷光铂配合物的理论研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-25 DOI: 10.1007/s00214-024-03107-y

Hadj Mezouar, Houari Brahim, Mostefa Boumediene, Fatima Yahia Cherif, Djebar Hadji, Abdelkrim Guendouzi

{"title":"Theoretical investigation on phosphorescent platinum complexes based on two tetradentate bipyridine ligands","authors":"Hadj Mezouar, Houari Brahim, Mostefa Boumediene, Fatima Yahia Cherif, Djebar Hadji, Abdelkrim Guendouzi","doi":"10.1007/s00214-024-03107-y","DOIUrl":"https://doi.org/10.1007/s00214-024-03107-y","url":null,"abstract":"In this work, the geometrical, optical, and phosphorescence properties of four complexes with general formula [dRpypy—C(OCH3)R′—dRpypy]Pt, with Pt-1 (R = F, R′ = methyl), Pt-2 (R = F, R′ = hexyl), Pt-3 (R = methoxy, R′ = methyl) and Pt-4 (R = methoxy, R′ = hexyl), were studied using the B3PW91 and TD-B3PW91 methods. The effect of the double substitution R and R′ on the electronic properties of the four complexes has been investigated. Replacing the two fluorine atoms with the two methoxy groups modifies the shape of the UV–vis spectra and red shift the phosphorescence spectra, while the substituents on the linker R′ do not induce changes in both absorption and phosphorescence spectra. Normal modes involved in the vibronic structure were identified and analyzed using adiabatic Hessian approaches according to the Franck–Condon approximation. The computed phosphorescence wavelengths agree with the observed ones and indicate that the fluorinated complexes exhibit a bright light blue color, while the methoxy complexes display a light spring green color. Further, temperature effects on simulated phosphorescence spectra were studied.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"13 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140303282","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}

引用次数: 0

Adsorption and separation effects of typical metal nuclides on the WS2 surface: a DFT study 典型金属核素在 WS2 表面的吸附和分离效应：DFT 研究

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-25 DOI: 10.1007/s00214-024-03108-x

Haifei Chen, Yawei Chen, Yongsheng Cui, Shaoyang Ren, Xuan Chen

{"title":"Adsorption and separation effects of typical metal nuclides on the WS2 surface: a DFT study","authors":"Haifei Chen, Yawei Chen, Yongsheng Cui, Shaoyang Ren, Xuan Chen","doi":"10.1007/s00214-024-03108-x","DOIUrl":"https://doi.org/10.1007/s00214-024-03108-x","url":null,"abstract":"The fission products brought about by the growth of nuclear energy is increasing, and their radioactivity will seriously jeopardize human health and pollute the environment. The recycling of radioactive materials has become a problem that needs to be solved nowadays. In this paper, we simulate the adsorption behaviors of typical fission products Cs, Sr, and Co on the surface of WS2 based on first-principle study. 3 × 3 supercell is selected by convergence test and calculate and compare the parameters of adsorption sites, adsorption energy, and charge transfer. At the microelectronic level, we analyze the interactions of WS2 with the three nuclides in detail. In addition, the effect of temperature on the adsorption rate of each nuclide on the WS2 surface is further evaluated by empirical equations. The results show that fissionable metal nuclides tend to be located at the top of the metal atoms of two-dimensional transition metal sulfides (top site of the W atom of WS2), and Co, moreover, has a much larger adsorption energy than that of Cs and Sr due to its binding to W in a form similar to covalent bonds. Moreover, under high temperature conditions, WS2 is more favorable for selecting Co and separating it from Cs and Sr. WS2 is expected to be an excellent material for the separation and recovery of radionuclide Co.","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":"26 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140299916","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}

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Foreword to the special issue on the “Electronic structure: principles and applications (ESPA 2022)” conference 电子结构：原理与应用（ESPA 2022）"会议特刊前言

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-22 DOI: 10.1007/s00214-024-03105-0

Manuel F. Ruiz-López, Angeles Peña-Gallego

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Size-dependent optical properties of [6]-, [8]- and [10]Cycloparaphenylene dications: the role of degenerate states 6]-、[8]- 和 [10]Cycloparaphenylene dications 大小相关的光学特性：退化态的作用

IF 1.7 4区化学

Theoretical Chemistry Accounts Pub Date : 2024-03-22 DOI: 10.1007/s00214-024-03106-z

Akhil Chakravarthy Kakarlamudi, Probal Nag, Sivaranjana Reddy Vennapusa

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