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Phenol Photostatic Spectra and Quantum-Classical Photodynamic Deprotonation 苯酚光静态光谱和量子经典光动力去质子化作用
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-22 DOI: 10.1002/qua.27504
Vladimir Pomogaev, Elena Bocharnikova, Olga Tchaikovskaya, Pavel Avramov

The spectral-luminescence properties and photochemical conversions of phenol were analyzed for an isolated molecule as well as in water solvents in a continuum implicit model and explicit atomistic surroundings. This involved employing cut-edge hybrid quantum-classical methodologies to generate static optical spectra and the excited dissipative crossing potential energy curves. A combination of electronic excitations, gradient calculations, and embedding electrostatic potential fitting charges on quantum-classical molecular dynamic propagation trajectories provided statistically averaged absorption spectra. The mixed-reference spin-flip multiconfigurational linear response method based on reference triplet preprocessed in the time-dependent density-functional theory was utilized to determine conical intersections between the lowest excited and ground states, as well as two-stage transitions from the second excitation to the ground state. Non-adiabatic quantum-classical molecular dynamics defined photodissipative trajectories of excited states, their lifetimes, and crossing points through trajectory surface hopping together with the mixed-reference spin-flip and embedding electrostatic potential fitting approaches. Dyson orbitals of the extended Koopmans' theorem were applied to reveal the nature of molecular states at conical intersections and key points on photodynamic trajectories. Potential hydroxyl group cleavage predicted with conical intersections searching turns to “swift” OH deprotonation through |π→σOH*$$ {upsigma}_{mathrm{OH}}^{ast } $$⟩ transition along photodynamic propagations in contrast with “long” processes leading to benzene ring deformation with stable OH bond.

在连续隐式模型和显式原子环境中,分析了孤立分子和水溶液中苯酚的光谱发光特性和光化学转换。这包括采用切边混合量子-经典方法生成静态光学光谱和激发耗散交叉势能曲线。电子激发、梯度计算和量子经典分子动力学传播轨迹上的静电势拟合电荷嵌入相结合,提供了统计平均吸收光谱。混合参考自旋翻转多配置线性响应法基于参考三重在时变密度函数理论中的预处理,用来确定最低激发态和基态之间的锥形交叉,以及从第二激发态到基态的两级转变。非绝热量子经典分子动力学定义了激发态的光耗散轨迹、其寿命,以及通过轨迹面跳跃和混合参考自旋翻转和嵌入静电位拟合方法确定的交叉点。应用扩展库普曼斯定理的戴森轨道揭示了分子状态在锥形交叉点和光动力轨迹关键点的性质。通过|π→ σ OH * $$ {upsigma}_{mathrm{OH}}^{ast },利用锥形交叉搜索预测的潜在羟基裂解变成了 "迅速 "的 OH 去质子化。$$ ⟩转变沿着光动力传播,与 "长 "过程形成对比,"长 "过程导致苯环变形,OH 键稳定。
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引用次数: 0
Investigating the Optoelectronic Properties of 2-D and 3-D CaTi1−xCuxO3 as a Phosphor Materials: A Density Functional Theory Approach 研究作为荧光粉材料的二维和三维 CaTi1-xCuxO3 的光电特性:密度泛函理论方法
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-21 DOI: 10.1002/qua.27486
Naqash H. Malik, Qaiser Rafiq, Muhammad Farooq Nasir, Sikander Azam, Muhammad Tahir Khan, Gaber A. M. Mersal, Mahmoud M. Hessien

The CaTiO3 has been extensively investigated as a highly promising optical material mostly for its optoelectronic properties and its function as a host for transition metals doped in the CaTiO3. Electronic and optical properties of CaTi1−xCuxO3 (2-D and 3-D) have been thoroughly analyzed using first-principles calculations based on Density Functional Theory (DFT). The calculations of these properties in both 2-D and 3-D configurations have performed by the use of generalized gradient approximation plus Hubbard (GGA + U). The electronic characteristics including the electronic band structure, partial density of states, and total density of states have been meticulously computed for CaTi1−xCuxO3 in both 2-D and 3-D. Upon analyzing the obtained results, we investigated that conduction and valence bands overlapped for both 2-D and 3-D structures revealing the metallic nature. We observed transitions mainly attributed to Cu-d, Ti-d, Ti-p, and O-p orbitals in both 2-D and 3-D configurations. Discussion delves into the significance of electronic band structure calculations in understanding optical properties. Peaks in the energy loss function are observed at 13 eV in both cases referred to the plasmon energy. Static values of the dielectric functions, extinction coefficient, reflectivity, and refraction are also computed. Our obtained results showed that the CaTi1−xCuxO3 compound in 3-D form is more apt for optoelectronic devices and UV-LED applications.

CaTiO3 作为一种极具发展前景的光学材料受到了广泛的研究,主要是因为它的光电特性和作为掺杂在 CaTiO3 中的过渡金属宿主的功能。基于密度泛函理论(DFT)的第一性原理计算对 CaTi1-xCuxO3 的二维和三维电子和光学特性进行了深入分析。这些特性在二维和三维构型中的计算都是通过使用广义梯度近似加哈伯德(GGA + U)进行的。对 CaTi1-xCuxO3 的电子特性,包括电子带结构、部分态密度和总态密度进行了细致的二维和三维计算。通过分析所获得的结果,我们发现二维和三维结构的导带和价带都有重叠,这揭示了其金属性质。我们观察到,在二维和三维结构中,跃迁主要归因于 Cu-d、Ti-d、Ti-p 和 O-p 轨道。讨论深入探讨了电子能带结构计算在理解光学特性方面的意义。在两种情况下,都能在 13 eV 处观察到能量损失函数的峰值,即等离子体能量。我们还计算了介电函数、消光系数、反射率和折射率的静态值。研究结果表明,三维形式的 CaTi1-xCuxO3 化合物更适合光电设备和紫外发光二极管的应用。
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引用次数: 0
Unveiling the Performance of SCAN Functional for Studying the Hydrated Ion in Solution: A Hybrid Forces Molecular Dynamics Study of La3+ Hydration 揭示 SCAN 函数在研究溶液中水合离子方面的性能:La3+ 水合的混合作用力分子动力学研究
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-18 DOI: 10.1002/qua.27499
Niko Prasetyo

SCAN/molecular mechanics molecular dynamics (SCAN/MM MD) simulations have been employed to investigate the structural and dynamical properties of La3+ in aqueous solution. These simulations revealed the presence of two distinct hydration shells, with the first shell exhibiting a La-O bond distance of 2.56 Å. The water molecules in this initial hydration shell displayed a mean residence time (MRT) of 208 ps, suggesting a less rigid structure. Five successful ligand exchange events occurred within a simulation duration of 100 ps. The stretching frequency of La-O was found to be 331 cm−1, with a force constant of 92 N/m. Notably, the data obtained from the SCAN/MM MD simulation demonstrated good agreement with experimental findings.

我们利用 SCAN/分子力学分子动力学(SCAN/MM MD)模拟研究了水溶液中 La3+ 的结构和动力学特性。这些模拟显示存在两个不同的水合壳,第一个水合壳的 La-O 键距离为 2.56 Å。水分子在这个初始水合壳中的平均停留时间(MRT)为 208 ps,表明其结构刚性较低。在 100 ps 的模拟持续时间内发生了五次成功的配体交换事件。发现 La-O 的伸展频率为 331 cm-1,作用力常数为 92 N/m。值得注意的是,SCAN/MM MD 模拟获得的数据与实验结果非常吻合。
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引用次数: 0
Investigating the Role of Anions in the Adsorption of Pyrrolidinium Based Ionic Liquids on Pt(111) Surface Using Density Functional Theory 利用密度泛函理论研究阴离子在吡咯烷基离子液体在铂(111)表面吸附过程中的作用
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-15 DOI: 10.1002/qua.27497
Arka Prava Sarkar

The adsorption properties of ionic liquids containing pyrrolidinium cations and various inorganic anions as electrolytes on a platinum surface were analyzed using first principle density functional theory. Three different orientations of the alkyl cation chain were observed during the adsorption process. The strength and structural stability varied between non-fluorinated and fluorinated anions upon adsorption, with oxygen atoms influencing the mechanism of adsorption and driving the structural stability of the anion, while fluorine atoms played a role in determining the orientation of the cation during adsorption. Net atomic charges analysis, electron density difference methods, and electron density accumulation for this complex system were utilized to further investigate these phenomena. The results of this study provide valuable insights into the role of anions in the adsorption behavior of pyrrolidinium-based ionic liquids on platinum surfaces, shedding light on the factors that influence their adsorption properties and structural stability on a molecular level. The findings of this study contribute to a better understanding of the interplay between anions and platinum surfaces in the adsorption of pyrrolidinium based ionic liquids, which can have implications for various applications such as electrochemistry, catalysis, and energy storage.

利用第一原理密度泛函理论分析了含有吡咯烷阳离子和各种无机阴离子的离子液体作为电解质在铂表面的吸附特性。在吸附过程中,观察到烷基阳离子链有三种不同的取向。非氟化阴离子和氟化阴离子在吸附时的强度和结构稳定性各不相同,氧原子影响吸附机理并驱动阴离子的结构稳定性,而氟原子在吸附过程中起着决定阳离子取向的作用。为了进一步研究这些现象,我们对这一复杂体系采用了净原子电荷分析、电子密度差法和电子密度累积法。本研究的结果为阴离子在吡咯烷基离子液体在铂表面的吸附行为中的作用提供了有价值的见解,从分子层面揭示了影响其吸附特性和结构稳定性的因素。这项研究的发现有助于人们更好地理解阴离子和铂表面在吡咯烷基离子液体吸附过程中的相互作用,从而对电化学、催化和能量储存等各种应用产生影响。
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引用次数: 0
Combinatory Effect of Gemcitabine and 5-Fluorouracil Investigated Through Chemoinformatics and Molecular Dynamics Simulation Against Breast Cancer 通过化疗信息学和分子动力学模拟研究吉西他滨和 5-氟尿嘧啶对乳腺癌的协同作用
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-14 DOI: 10.1002/qua.27498
Sureba Sukumaran, Azar Zochedh, Kaliraj Chandran, Asath Bahadur Sultan, Thandavarayan Kathiresan

Co-delivering FDA-approved drugs can be less harmful and boost biological activity by targeting different protein mechanism at same time. Gemcitabine and 5-Fluorouracil (GE5F) adduct work together to destroy cancer cells and increase the efficacy in the fight against breast cancer. The basis set B3LYP/6-311 G was utilized in this investigation to improve the structure of GE5F adduct. The natural bond analysis exhibited the intermolecular interactions of the GE5F adduct. Electronic transitions were seen to be π → π*, and theoretical calculations were performed for the ultraviolet to visible spectrum. The energy gap between HOMO and LUMO was used to study the GE5F adduct's structural stability and reactivity; the computed energy gap (ΔE) was 3.912 eV. The Mulliken charge population was assessed and the complex structure's electrostatic potential was established. Weak interactions of the GE5F were assessed using RDG analysis, and topological aspects were investigated using LOL and ELF analysis. Investigating the GE5F adduct's adsorption, distribution, metabolism, excretion, and toxicity properties, the results confirmed that GE5F adduct comes under the safety parameters being a drug-likeness molecule. Molecular docking experiments were conducted using target proteins for breast cancer. The complex molecule had a higher binding affinity as indicated by the docking scores, which validated the better combinatorial interaction between gemcitabine and 5-Fluorouracil. With − 9.4 kcal/mol, the complex molecule's strongest binding capacity was against PARP protein, and stable confirmation was observed through molecular dynamic simulation for 100 ns with four hydrogen bond interactions. These in silico finding will pave a way for in vitro and in vivo experiments with better enhancement of FDA approved drugs.

同时靶向不同的蛋白质机制,可以减少对人体的伤害并提高生物活性。吉西他滨和 5-氟尿嘧啶(GE5F)加合物能共同摧毁癌细胞,提高抗击乳腺癌的疗效。本研究利用基集 B3LYP/6-311 G 改进了 GE5F 加合物的结构。自然键分析显示了 GE5F 加合物的分子间相互作用。电子跃迁为 π → π*,并对紫外至可见光谱进行了理论计算。利用 HOMO 和 LUMO 之间的能隙来研究 GE5F 加合物的结构稳定性和反应活性;计算得出的能隙 (ΔE) 为 3.912 eV。对 Mulliken 电荷群进行了评估,并确定了复合结构的静电位。利用 RDG 分析评估了 GE5F 的弱相互作用,并利用 LOL 和 ELF 分析研究了拓扑方面的问题。对 GE5F 加合物的吸附、分布、代谢、排泄和毒性特性进行了研究,结果证实 GE5F 加合物属于药物相似分子,符合安全参数。利用乳腺癌靶蛋白进行了分子对接实验。从对接得分来看,复合物分子具有更高的结合亲和力,这验证了吉西他滨和 5-氟尿嘧啶之间更好的组合相互作用。复合物分子与 PARP 蛋白的结合力最强,为-9.4 kcal/mol,通过分子动态模拟 100 ns,观察到四个氢键相互作用,复合物分子的结合力得到了稳定的证实。这些硅学发现将为体外和体内实验铺平道路,从而更好地提高 FDA 批准药物的疗效。
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引用次数: 0
DFT Analysis of Transition Metal (TM) Substitutions on Cu-Based Chalcogenides: Structural, Electronic, and Thermophysical Properties for Interface Thermal Performance and Energy 铜基钙钛矿上过渡金属 (TM) 取代的 DFT 分析:界面热性能和能量的结构、电子和热物理性质
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-12 DOI: 10.1002/qua.27500
Zeesham Abbas, Shafaat Hussain Mirza, Amna Parveen, Muhammad Aslam, Anatoly Zatsepin, Abdelmohsen A. Nassani

The current investigation employs first-principles DFT (density functional theory) calculations to examine the influence of transition metal replacements on the structural, thermodynamic, and thermoelectric properties of Cu-based chalcogenides TMCu3Se4 (TM = Nb/Ta/V). The PBE-generalized gradient approximation (GGA) model is utilized to compute the fundamental properties of Cu-based chalcogenides under study. A thorough examination of the energy band structures indicates that these chalcogenides are semiconductor compounds with indirect energy bandgaps. We can infer from the calculated energy band structures that the bandgap values are 1.67, 1.77, and 1.05 eV for NbCu3Se4, TaCu3Se4, and VCu3Se4, respectively. The ZTe$$ {mathrm{ZT}}_e $$ values for NbCu3Se4, TaCu3Se4, and VCu3Se4 are 0.661, 0.998, and 0.996, respectively. These values make them highly appropriate for usage in thermoelectric (TE) devices. The thermoelectric characteristics of pyrochlore oxides TMCu3Se4 (TM = Nb/Ta/V) suggest that these materials have promising potential for energy-related applications. The analyzed thermodynamic properties demonstrate that the Cu0based chalcogenide materials TMCu3Se4 (TM = Nb/Ta/V) exhibit a notable level of thermal stability.

目前的研究采用第一原理 DFT(密度泛函理论)计算,考察了过渡金属置换对铜基瑀 TMCu3Se4(TM = Nb/Ta/V)的结构、热力学和热电性能的影响。本研究利用 PBE 广义梯度近似(GGA)模型计算所研究的铜基瑀的基本性质。对能带结构的深入研究表明,这些瑀是具有间接能带隙的半导体化合物。从计算得到的能带结构可以推断,NbCu3Se4、TaCu3Se4 和 VCu3Se4 的带隙值分别为 1.67、1.77 和 1.05 eV。NbCu3Se4、TaCu3Se4 和 VCu3Se4 的 ZT e $$ {mathrm{ZT}}_e $$ 值分别为 0.661、0.998 和 0.996。这些数值使它们非常适合用于热电(TE)设备。热长石氧化物 TMCu3Se4(TM = Nb/Ta/V)的热电特性表明,这些材料在能源相关应用方面具有广阔的发展前景。热力学特性分析表明,基于 Cu0 的 Chalcogenide 材料 TMCu3Se4 (TM = Nb/Ta/V)具有显著的热稳定性。
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引用次数: 0
Theoretical Study on the Dissociation Mechanism of Thiophene in the UV Photoabsorption, Ionization, and Electron Attachment Processes 紫外光吸收、电离和电子附着过程中噻吩解离机理的理论研究
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-10 DOI: 10.1002/qua.27503
Hari P. Upadhyaya

A computational study on the intricate mechanism of thiophene ring-fragmentation (TRF) in the UV photodissociation, dissociative ionization, and dissociative electron attachment process has been performed. The complete fragmentation process is studied using high level G4 composite method for neutral, cationic, and anionic species by elucidating a detailed mechanism for various reaction channels. The study shows that for neutral thiophene, the major pathway is the migration of H atom and subsequent fragmentation through a transition state yielding acetylene (HC≡CH) and H2C=C=S. However, for the thiophene cation, the acetylene (HC≡CH)+H2C=C=S+ channel is a two-step and barrier less process. The onset of CH3+HC=C=C=S channel has been observed in both the thiophene cation and anion which was absent in the neutral analogue. Similarly, the onset of H2S+HC≡C—C≡CH channel has been found to operate only in the thiophene cation. Others, such as HCS and HS elimination channels have been found in all the species showing similar dissociation mechanism. For the thiophene anion, the TRF process is very much similar to that of thiophene cation. However, the reaction enthalpies of the various elimination channels in the anionic species are lower as compared to that of cationic species. During the study, the ionization energies and electron affinities of various molecules/radicals produced during the fragmentation process of thiophene were also computed.

对噻吩环破碎(TRF)在紫外光解离、离解电离和离解电子附着过程中的复杂机理进行了计算研究。通过阐明各种反应通道的详细机理,采用高水平 G4 复合方法研究了中性、阳离子和阴离子物种的完整破碎过程。研究表明,对于中性噻吩,主要途径是 H 原子迁移,随后通过过渡态碎裂生成乙炔(HC≡CH)和 H2C=C=S。然而,对于噻吩阳离子,乙炔(HC≡CH)+H2C=C=S+ 通道是一个两步且障碍较少的过程。噻吩阳离子和阴离子中都出现了 CH3+HC=C=C=S 通道,而中性类似物中则没有。同样,H2S+HC≡C-C≡CH 通道只在噻吩阳离子中起作用。其他通道,如 HCS 和 HS 消除通道,在所有物种中都有发现,显示出类似的解离机制。对于噻吩阴离子,TRF 过程与噻吩阳离子非常相似。不过,阴离子物种中各种消除通道的反应焓要低于阳离子物种。在研究过程中,还计算了噻吩破碎过程中产生的各种分子/自由基的电离能和电子亲和力。
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引用次数: 0
α,β-C—C—C Agostic Bonding Interactions in Ruthenacyclobutane and π-Complex Assisted Olefin Metathesis Catalyzed by Ruthenium-Alkylidene Complexes 钌-亚烷基络合物催化的钌环丁烷和 π-络合物辅助烯烃 Metathesis 中的α、β-C-C-C Agostic Bonding 相互作用
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-08 DOI: 10.1002/qua.27493
Carmen-Irena Mitan, Valerian Dragutan, Petru Filip

Computational aspects of concerted [2+2] oxidative-retrocycloaddition-cycloreversion reaction through ruthenium alkylidene π-complexes and ruthenacyclobutane with α,β-(C—C—C) agostic bonding interactions in olefin metathesis are presented. d6-Ruthenium carbene complexes, with ruthenium in the oxidation state +2, undergo successive [2+2] cycloaddition and cycloreversion steps, through associative, dissociative, or interchange mechanisms. This process involves coordination of the olefin to 16-electron Ru complex followed by phosphine dissociation, or first phosphine dissociation then coordination of the olefin to the 14-electron Ru complex with rearrangement to a ruthenacyclobutane intermediate, followed by symmetrical reverse steps. Donation of σ-electron density from the two C—C σ-bonds to the metal center leads to α,β-(C—C—C) agostic bonds, which stabilized metallacyclobutane as a formally 16-electron complex, with lower energy than the corresponding π-complex. In the transformation from π-complex to ruthenacyclobutane the ruthenium atom is formally oxidized to Ru(IV). The most efficient ligands are those that stabilize the high-oxidation state metallacyclobutane (IV) intermediate relative to the ruthenium carbene.

介绍了在烯烃复分解反应中,通过亚烷基钌π络合物和具有α,β-(C-C-C) agostic 键相互作用的环丁烷与钌发生协同[2+2]氧化-还原环加成-环氧化反应的计算问题。d6 碳化钌配合物中的钌处于氧化态 +2,通过缔合、离解或交换机制连续进行 [2+2] 环加成和环转化步骤。这一过程包括烯烃与 16 电子 Ru 复合物配位,然后膦解离,或者先是膦解离,然后烯烃与 14 电子 Ru 复合物配位,重排成钌环丁烷中间体,接着是对称的反向步骤。σ电子密度从两个 C-C σ键捐献给金属中心,导致α,β-(C-C-C)激动键,从而使金属环丁烷稳定为形式上的 16 电子络合物,其能量低于相应的 π-络合物。在从π-络合物转化为鲁钌环丁烷的过程中,钌原子被正式氧化为 Ru(IV)。最有效的配体是那些相对于碳化钌能稳定高氧化态金属环丁烷(IV)中间体的配体。
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引用次数: 0
Computational Study of the Formation of Atmospheric Aerosol Precursors Under Ambient Conditions: A Case Study of the Interaction Between Sea Salt, Water, and Sulfuric Acid Molecules 环境条件下大气气溶胶前体形成的计算研究:海盐、水和硫酸分子之间相互作用的案例研究
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-08 DOI: 10.1002/qua.27489
Dhyani Vadgama, Rohit Srivastava, Satyam Shinde

Cluster formation has significant implications in atmospheric science and environmental chemistry. These clusters are characterized by complex interactions between their constituents, which influence their structure, stability, and growth. Experimental investigations are difficult for the initial stages of prenucleation cluster formation, which leads to larger aerosols. To understand the formation of clusters, the interactions between sea salts (NaCl, KCl, and MgCl2), water, and sulfuric acid molecules have been investigated. Each step has been comprehensively examined and thermodynamic parameters have been computed using DLPNO-CCSD(T)/CBS//M06-2X/6-311++G(3df,3pd) to find the stabilities of the molecular complexes. Among all complexes, the binding energies of cluster (SS)1(W)1(SA)3 are found to be the lowest due to the formation of HCl, hydrogen bonding, and weak van der Waal forces. Sea salts have shown a more favorable interaction with H2SO4 compared to H2O molecules. The addition of H2SO4 increases the reactivity of the cluster (SS)1(W)n, while the addition of H2O molecules reduces the reactivity of the cluster (SS)1(SA)n. However, further addition of H2SO4 or H2O to the existing cluster (SS)1(W)n(SA)n increases the free energy of formation. Furthermore, the influence of temperature was also investigated, suggesting that complex formation is slightly more favorable at lower temperatures than at higher temperatures. The negative values of thermodynamic parameters indicate, that these complexes are spontaneous and exothermic over the colder regions.

团簇的形成对大气科学和环境化学具有重要影响。这些团聚体的特点是其成分之间存在复杂的相互作用,从而影响其结构、稳定性和生长。对于导致较大气溶胶形成的预核团簇形成的初始阶段,很难进行实验研究。为了了解气溶胶团的形成过程,我们对海盐(氯化钠、氯化钾和氯化镁)、水和硫酸分子之间的相互作用进行了研究。对每个步骤都进行了全面研究,并使用 DLPNO-CCSD(T)/CBS//M06-2X/6-311++G(3df,3pd)计算了热力学参数,以找出分子络合物的稳定性。在所有络合物中,发现簇(SS)1(W)1(SA)3 的结合能最低,原因是形成了 HCl、氢键和弱范德华力。与 H2O 分子相比,海盐与 H2SO4 的相互作用更为有利。加入 H2SO4 会提高簇(SS)1(W)n 的反应活性,而加入 H2O 分子则会降低簇(SS)1(SA)n 的反应活性。然而,在现有的簇 (SS)1(W)n(SA)n 中进一步添加 H2SO4 或 H2O 会增加形成的自由能。此外,我们还研究了温度的影响,结果表明,低温比高温更有利于络合物的形成。热力学参数的负值表明,这些络合物是自发形成的,在较冷区域会放热。
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引用次数: 0
Study of the Torquoselectivity of a Set of Unusual Ring-Opening Electrocyclic Reactions: Determination of the Electronic Bonding Structure Through the Methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, and Analysis of the Electronic Reaction Mechanism Through Bond Reactivity Descriptors 一组不寻常开环电环反应的环选择性研究:通过自然键轨道分析和分子中原子的量子理论确定电子键结构,并通过键反应性描述符分析电子反应机理
IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2024-10-07 DOI: 10.1002/qua.27494
Jesús Sánchez-Márquez, Alejandro Morales-Bayuelo

In this work, we have studied the torquoselectivity of a set of unusual ring-opening electrocyclic reactions that have not been successfully rationalized using models based on orbital symmetry nor have they been explained by steric hindrance. Firstly, the corresponding transition states have been obtained, and it has been verified that the intrinsic reaction coordinates associated with these transition states are consistent with the reactants and products of the reactions studied. This has allowed us to theoretically calculate the reaction barriers (with their corresponding thermal corrections) and compare them with the corresponding experimental values. In a second step, we have analyzed the electronic bonding structure using the methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, searching for interactions that may significantly stabilize the transition states. Finally, we have analyzed the reactivity using a recent model that has allowed us to calculate the corresponding bond reactivity descriptors.

在这项工作中,我们研究了一组不寻常的开环电环反应的转折选择性,这些反应既没有成功地用基于轨道对称性的模型来合理解释,也没有用立体阻碍来解释。首先,我们获得了相应的过渡态,并验证了与这些过渡态相关的固有反应坐标与所研究反应的反应物和产物是一致的。这样,我们就可以从理论上计算反应壁垒(及其相应的热修正),并将其与相应的实验值进行比较。第二步,我们利用自然键轨道分析和分子中原子量子理论的方法分析了电子键结构,寻找可能显著稳定过渡态的相互作用。最后,我们利用一个最新模型分析了反应性,该模型使我们能够计算相应的键反应性描述符。
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引用次数: 0
期刊
International Journal of Quantum Chemistry
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