Computational and Theoretical Chemistry最新文献

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DFT-based, Monte Carlo and Grand Canonical Monte Carlo simulations of nitro-organic pollutants 4-nitrophenol, 2-nitrophenol, 9-nitroanthracene and nitrogen trifluoride interacting with water in zeolite imidazole framework (ZIF-8) 基于 DFT、蒙特卡洛和大卡农蒙特卡洛模拟硝基有机污染物 4-硝基苯酚、2-硝基苯酚、9-硝基蒽和三氟化氮在沸石咪唑框架 (ZIF-8) 中与水的相互作用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.comptc.2024.114995

Celia Adjal , Nabila Guechtouli , Vicente Timón , Rahma Boussassi , Dalila Hammoutène , María Luisa Senent

We report in this study the behaviour of adsorbed Nitrogen-volatile organic compounds (NVOCs) such as 2NP (2-Nitrophenol), 4NP (4-Nitrophenol), 9NAnt (9-Nitroanthracene), NF₃ (Nitrogen trifluoride) with and without water in Zinc-Imidazolate Framework (ZIF-8) using the Density Functional Theory (DFT). The work considers both single and multiple molecular capture of different species of pollutants, along with theoretical research based on force fields to determine the maximum number of molecules that can be loaded inside the material. Negative adsorption energy is obtained when each pollutant is considered separately or in mixtures. The values range from −2.6 kJ/mol to −137.1 kJ/mol depending on the size of adsorbed species. Modelling of the adsorbed pollutants on ZIF-8 towards the use of the code CASTEP show the possible interaction with the imidazole rings of the bulk crystal. The interaction energy (E_int) indicates that the capture of 2NP and 4NP is more favourable with H₂O than 9NAnt and NF₃. More specifically, E_int corresponding to one water molecule with one pollutant (4NP, 2NP, 9NAnt, NF₃) is −0.473, −5.580, +0.588, and +8.307 kJ/mol, respectively. The Connolly surface was calculated to gain a better understanding of the volume and surface accessibility of ZIF-8, which helps to predict and support CASTEP results. Finally, an isotherm study was conducted using a Monte Carlo simulation, which proved useful in interpreting the most probable mechanism of the competing mixed capture. The results obtained were similar to those provided by Density Functional Theory (DFT).

在本研究中，我们利用密度泛函理论（DFT）报告了在锌咪唑框架（ZIF-8）中吸附氮挥发性有机化合物（NVOC）（如 2NP（2-硝基苯酚）、4NP（4-硝基苯酚）、9NAnt（9-硝基蒽）、NF3（三氟化氮）（含水和不含水）的行为。这项研究同时考虑了不同种类污染物的单分子和多分子捕获，以及基于力场的理论研究，以确定材料内部可装载的最大分子数量。当单独考虑每种污染物或混合物时，都会得到负吸附能。根据吸附物种的大小，吸附能的数值从 -2.6 kJ/mol 到 -137.1 kJ/mol 不等。使用 CASTEP 代码对 ZIF-8 上吸附的污染物进行建模，结果表明可能会与块状晶体的咪唑环发生相互作用。相互作用能（Eint）表明，2NP 和 4NP 与 H2O 的捕获比 9NAnt 和 NF3 更有利。更具体地说，一个水分子与一种污染物（4NP、2NP、9NAnt 和 NF3）的相互作用能分别为 -0.473、-5.580、+0.588 和 +8.307 kJ/mol。通过计算 Connolly 表面，可以更好地了解 ZIF-8 的体积和表面可达性，这有助于预测和支持 CASTEP 结果。最后，利用蒙特卡洛模拟进行了等温线研究，这有助于解释竞争性混合捕获的最可能机制。获得的结果与密度泛函理论（DFT）提供的结果相似。

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引用次数: 0

Investigation of the adsorption behavior of the adenine nucleobase molecules on the WS2 nanosheets and their transition metal (Co, Ni) modified structures via DFT 通过 DFT 研究腺嘌呤核碱基分子在 WS2 纳米片及其过渡金属（Co、Ni）修饰结构上的吸附行为

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-13 DOI: 10.1016/j.comptc.2024.114983

Farag M.A. Altalbawy , Uday Abdul-Reda Hussein , Soumya V. Menon , Anjan Kumar , Bharti Kumari , Rajni Verma , G.V. Siva Prasad , Mohammed Ayad Alboreadi , Zainab Ahmed Hamodi , Hussein Ghafel Shakie , Muthna kereem

In this work, the adsorption and sensing properties of adenine nucleobases on the surface of WS₂ nanosheets modified with Co and Ni transition metals have been examined using the density functional theory (DFT) calculations. The adsorption energies and optimum distances of nucleobases towards the modified nanostructures have been evaluated to describe the structural stability. Because of negative and large adsorption energies, all the adsorption processes are spontaneous with chemisorption nature. Smaller band gap of the Co and Ni modified WS₂ nanosheets indicates relatively improved conductivity of these nanostructures compared with the pristine system. Based on spin-polarized calculations, the Co and Ni functionalized WS₂ nanosheets exhibit magnetic properties with large magnetic moments. This investigation demonstrated that Co and Ni modified WS₂ substrates possess superior sensing properties as compared to the pristine ones. Therefore, the sensor nanomaterial may be strongly utilized in detecting and biosensing of adenine nucleobases.

在这项研究中，利用密度泛函理论（DFT）计算研究了腺嘌呤核碱基在钴和镍过渡金属修饰的 WS2 纳米片表面的吸附和传感特性。评估了核碱基对修饰纳米结构的吸附能和最佳吸附距离，以描述其结构稳定性。由于吸附能为负且较大，所有的吸附过程都是自发的化学吸附过程。与原始体系相比，钴和镍修饰的 WS2 纳米片的带隙较小，这表明这些纳米结构的导电性相对较好。根据自旋极化计算，Co 和 Ni 功能化的 WS2 纳米片具有大磁矩的磁性。这项研究表明，与原始 WS2 相比，Co 和 Ni 修饰的 WS2 基底具有更优越的传感性能。因此，这种传感器纳米材料可在腺嘌呤核碱基的检测和生物传感方面发挥重要作用。

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引用次数: 0

Role of substitution Zr-site on the electronic structure and magnetic properties of BaTiO3 materials: A first principles calculation 取代的 Zr 位对 BaTiO3 材料的电子结构和磁性能的影响：第一原理计算

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-13 DOI: 10.1016/j.comptc.2024.114989

Vu Tien Lam , Nguyen Huu Lam , Duong Quoc Van , Nguyen Hoang Thoan , Nguyen Ngoc Trung , Dang Duc Dung

In this study, we employ density functional theory calculations to investigate the electronic band structures, density of states, and magnetic properties of pure BaTiO₃ and Zr-doped BaTiO₃ compounds. The intrinsic BaTiO₃ compound exhibits an indirect band gap of 1.80 eV, which is larger than the range of 1.61–1.71 eV observed for Zr-doped BaTiO₃. By systematically exploring the Zr substitution at different Ti sites, we analyze the impact of Zr doping on the electronic structure of BaTiO₃ materials. The introduction of Zr doping induces significant modifications in the band structure and density of states, resulting in the emergence of new energy levels within the band gap. These findings enhance the understanding of the electronic properties of BaTiO₃ and Zr-doped BaTiO₃ materials, paving the way for potential applications in electronic and optical devices.

在本研究中，我们采用密度泛函理论计算来研究纯 BaTiO3 和掺杂 Zr 的 BaTiO3 化合物的电子能带结构、状态密度和磁性能。本征 BaTiO3 化合物的间接带隙为 1.80 eV，大于掺杂 Zr 的 BaTiO3 的 1.61-1.71 eV。通过系统地探索 Zr 在不同 Ti 位点的取代情况，我们分析了掺杂 Zr 对 BaTiO3 材料电子结构的影响。掺杂 Zr 会显著改变带状结构和态密度，从而在带隙内出现新的能级。这些发现加深了人们对 BaTiO3 和掺杂 Zr 的 BaTiO3 材料电子特性的理解，为其在电子和光学设备中的潜在应用铺平了道路。

引用次数: 0

Catalytic pyrolysis mechanism of tetrabromobisphenol A by calcium oxide: A density functional theory study 氧化钙催化四溴双酚 A 的热解机理：密度泛函理论研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114987

Jiankai Ou , Lufang Zhao , Yang Long , Yu Jiang , Xin Mu , Jinbao Huang , Hong Wang

In this paper, the mechanisms of catalytic pyrolysis of tetrabromobisphenol A (TBBPA) by calcium oxide (CaO) were studied through density functional theory methods. The results indicate that the phenolic hydroxyl group of TBBPA is the preferred site for CaO to extract protons, and the generated anion further transforms into 2,6-dibromophenol via demethylation and hydrogen transfer reactions. The reaction activity of CaO with hydrogen bromide is relatively high, with an energy barrier of 133.2 kJ/mol. CaO produces calcium ions, which combine with bromine ions to form calcium bromide to achieve the purpose of fixing bromine. In addition, the participation of calcium ions results in the OH bond being easier to crack, which further lowers the reaction energy barrier of keto-enol tautomerism reactions H₂O produced during catalytic pyrolysis also has an obvious catalytic effect, and the energy barrier of the keto-enol tautomerism reaction decreased from 309.1 kJ/mol to 150.6 kJ/mol with the participation of H₂O.

本文通过密度泛函理论方法研究了氧化钙（CaO）催化热解四溴双酚 A（TBBPA）的机理。结果表明，四溴双酚 A 的酚羟基是 CaO 提取质子的首选位点，生成的阴离子通过脱甲基和氢转移反应进一步转化为 2,6-二溴苯酚。CaO 与溴化氢的反应活性相对较高，能垒为 133.2 kJ/mol。CaO 生成钙离子，钙离子与溴离子结合生成溴化钙，从而达到固定溴的目的。此外，钙离子的参与使 OH 键更容易裂开，从而进一步降低了酮烯醇同分异构反应的反应能垒。催化热解过程中产生的 H2O 也具有明显的催化作用，在 H2O 的参与下，酮烯醇同分异构反应的能垒从 309.1 kJ/mol 降至 150.6 kJ/mol。

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引用次数: 0

Cation–anion chalcogen bonds in ion pairs: A combined crystallographic survey and computational investigation 离子对中的阳离子-阴离子缩醛键：晶体学调查与计算研究的结合

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114985

Hui Liu , Zijian Han , Yunxiang Lu , Zhijian Xu , Weiliang Zhu

Cation–anion chalcogen bonds (ChBs) have been frequently observed in the X-ray crystals of the salts formed by chalcogenated cations and a diversity of anions. In this work, we first collected a huge number of crystal structures consisting of cation–anion ChBs from the Cambridge Structural Database (CSD). Then, a set of ion-pairing complexes of chalcogenated cations with four anions (Cl⁻, Br⁻, I⁻ and NO₃⁻) were selected to study such interactions found in crystal structures. Owing to the much short bonding distances and the considerably large absolute binding energies, cation–anion ChBs in the complexes are very strong, leading to some degree of covalency. These interactions are directional both in solid state and in gas phase, and heavier ChBs tend to have a higher covalent content. As revealed by energy decomposition analysis, the orbital term has an important contribution to the attraction of ChBs between cations and anions.

在由钙化阳离子和多种阴离子形成的盐的 X 射线晶体中，经常可以观察到阳离子-阴离子钙原键（ChBs）。在这项工作中，我们首先从剑桥结构数据库（CSD）中收集了大量由阳离子-阴离子 ChBs 组成的晶体结构。然后，我们选择了一组铬化阳离子与四种阴离子（Cl-、Br-、I- 和 NO3-）的离子配对复合物，以研究晶体结构中发现的此类相互作用。由于成键距离很短，绝对结合能相当大，这些配合物中的阳离子-阴离子 ChBs 非常强，因而具有一定程度的共价性。这些相互作用在固态和气相中都是定向的，较重的 ChB 往往具有较高的共价含量。能量分解分析表明，轨道项对阳离子和阴离子之间 ChBs 的吸引力有重要作用。

引用次数: 0

Research on N, Ne, and P adsorption on boron-germanene nanoribbons for nano sensor applications 用于纳米传感器应用的硼-锗纳米带对 N、Ne 和 P 的吸附研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114988

Hoang Van Ngoc, Huynh Thi Phuong Thuy

The study investigated the adsorption of N, P, and Ne atoms on boron-germanene nanoribbons (BGeNRs) using density functional theory (DFT) and the Vienna Ab initio Simulation Package (VASP). Results indicated that both the pristine and adsorbed configurations exhibited metallic behavior. While the pristine and Ne-adsorbed configurations were nonmagnetic, the N- and P-adsorbed configurations displayed magnetic moments of 1.81 μ_B and 1.21 μ_B, respectively. The N-adsorbed configuration had the lowest adsorption energy, whereas the Ne-adsorbed configuration exhibited a positive adsorption energy. Multi-orbital hybridization analysis revealed that hybridization processes predominantly occurred in the conduction band at energy levels corresponding to the σ bond. Charge density difference analysis showed significant charge transfer between the substrate and the adsorbed elements. Additionally, optical properties, including the real and imaginary parts of the dielectric function, absorption coefficient, and electron-hole density, were systematically examined to highlight the variations. The findings underscore the potential application of BGeNR materials in nanosensors.

该研究利用密度泛函理论（DFT）和维也纳 Ab initio 仿真软件包（VASP）研究了 N、P 和 Ne 原子在硼-锗纳米带（BGeNRs）上的吸附。结果表明，原始构型和吸附构型都表现出金属特性。原始构型和Ne吸附构型没有磁性，而N和P吸附构型的磁矩分别为1.81 μB和1.21 μB。N 吸附构型的吸附能最低，而 Ne 吸附构型的吸附能为正值。多轨道杂化分析表明，杂化过程主要发生在导带中与σ键对应的能级上。电荷密度差分析表明，基底和吸附元素之间存在明显的电荷转移。此外，还系统地研究了光学特性，包括介电常数的实部和虚部、吸收系数和电子-空穴密度，以突出这些变化。这些发现强调了 BGeNR 材料在纳米传感器中的潜在应用。

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引用次数: 0

Geometrical features and chemical adsorptions of (Ag3Sn)n clusters (Ag3Sn)n 簇的几何特征和化学吸附作用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114986

Qiman Liu , Manli Zhang

The Ag-Sn alloys are famous ancient intermetallics, with the Ag₃Sn being a crucial component of the phase diagram. Recently, Ag₃Sn nanoparticles showcase efficient catalytic CO oxidation capabilities. Here, structural features and stability of (Ag₃Sn)_n (n = 1–6) clusters are first analyzed in detail. The results reveal that structures of them evolve from cages to close-packed icosahedra, where Ag are distributed on cores and gradually aggregated, whereas Sn occupy edge positions and become dispersed. Moreover, the icosahedral (Ag₃Sn)₃ has a higher stability than that of its neighbors and can maintain the structural integrity at 700 K. The molecular orbitals reveal that the (Ag₃Sn)₃ has an electronic open-shell configuration of 1S²1P⁶1D¹⁰2S²1F¹, which is confirmed by the density of states. Electrostatic potential surfaces show that (Ag₃Sn)_n have significant electron-deficient σ-hole regions at Ag sites, which can make CO stretching frequencies and bond lengths have red-shifts. Adsorption energies between (Ag₃Sn)_n and CO display odd–even oscillations, ranging from (0.43–0.68) eV, and the direction of charge flows is from CO → clusters. Our work provides inferences to structure evolutions and adsorptions of the Ag₃Sn alloy at the atomic level.

Ag-Sn合金是著名的古老金属间化合物，其中Ag3Sn是相图的重要组成部分。最近，Ag3Sn 纳米颗粒展示了高效的催化 CO 氧化能力。本文首次详细分析了 (Ag3Sn)n （n = 1-6）团簇的结构特征和稳定性。结果表明，它们的结构从笼状演化为紧密堆积的二十面体，其中银分布在核心并逐渐聚集，而锡占据边缘位置并变得分散。分子轨道显示，(Ag3Sn)3 的电子开壳构型为 1S21P61D102S21F1。静电位面显示(Ag3Sn)n在Ag位点上有明显的缺电子σ空穴区，这会使CO伸展频率和键长发生红移。(Ag3Sn)n与CO之间的吸附能呈现奇偶振荡，范围在(0.43-0.68)eV之间，电荷流的方向是从CO→簇。我们的工作提供了原子水平上 Ag3Sn 合金结构演变和吸附的推论。

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引用次数: 0

Binuclear complexes of all first row 3d metals (Sc to Zn) with a cyclic N4-tetradentate ligand: metal-metal bond strengths and bond orders 所有第一排 3d 金属（Sc 至 Zn）与环状 N4-十四酸酯配体的双核配合物：金属-金属键强度和键序

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114944

Salma Sultana, R.H. Duncan Lyngdoh

Metal-metal (MM) bonds in binuclear complexes M₂L₂ (L = tetradentate ligand) for the first row transition metals are studied using DFT to design novel complexes which mimic lantern complexes having four bidentate ligands. Two orientations for the ligand array are applied − orthogonal (orth) and lateral (lat). Ground states for all complexes are identified from several low-lying spin states, where each orth isomer is generally lower in energy than the corresponding lat isomer. All the MM bonds are assigned formal bond order (fBO) values through MO analysis and/or electron counting. The M₂L₂ orth complexes in many ways mimic the geometrical and electronic structure of known tetragonal lantern complexes. The formal shortness ratio (FSR) and the Wiberg index W_MM for the MM bond correlate well with the fBO values, validating their use as measures of intrinsic MM bond strength.

利用 DFT 研究了第一排过渡金属的双核配合物 M2L2（L = 四价配体）中的金属-金属（MM）键，从而设计出模仿具有四个双价配体的灯笼配合物的新型配合物。配体阵列有两个方向--正交（orth）和侧向（lat）。所有配合物的基态都是从几个低洼自旋态中确定的，其中每个正交异构体的能量通常低于相应的侧交异构体。通过 MO 分析和/或电子计数，为所有 MM 键分配了形式键序（fBO）值。M2L2 正交配合物在许多方面都模仿了已知四方灯笼配合物的几何和电子结构。MM 键的形式短度比（FSR）和威伯格指数 WMM 与 fBO 值相关性很好，这证明它们可以用来衡量 MM 键的内在强度。

引用次数: 0

Influence of 2,1,3-pyrazinochalcogenadiazoles structure on their dimerization via chalcogen bonding (chalcogen = S, Se, Te) 2,1,3-吡嗪基胆原二唑结构对其通过胆原键（胆原 = S、Se、Te）进行二聚化的影响

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-09 DOI: 10.1016/j.comptc.2024.114984

Qiaoyu Wei , Hui Wang , Andrey V. Zibarev

Chalcogen bonding (ChB) is an σ-hole-driven secondary bonding interaction (SBI). The crystalline 2,1,3-benzochalcogenadiazoles involved in organic optoelectronics is exemplified by [E···N]₂ supramolecular synthon. For 5,6- R₂ −2,1,3-pyrazinochalcogenadiazoles E-M and [E···N]₂-bonded (E-M)₂ (E = S, Se, Te; R/M = H/1, Me/2, CN/3), gas-phase and dichloromethane solution calculations are performed. The molecular electrostatic potential suggests that changes in E, R influence σ- and π-holes of E-M/(E-M)₂. Distant R acts via long-range electrostatic field effect. ChB strength increases in the order S < Se < Te, and (E-2)₂ < (E-1)₂ < (E-3)₂. The main driving forces are electrostatic and dispersion interactions. Crystalline S-1 and Se-2 have head-to-head dimers. Se-3 shows head-to-tail chains via Se···N_cyano ChB. A competition between different ChB, and, between ChB and other SBIs, should be considered in the design and synthesis of new E-M/(E-M)₂ for fundamentals and applications.

钙原键（ChB）是一种由σ-孔驱动的次键相互作用（SBI）。有机光电子学中涉及的 2,1,3-苯并羰基噻唑结晶是[E--N]2 超分子合成的典范。研究人员对 5,6- R2 -2,1,3-吡嗪基喹二唑 E-M 和 [E---N]2 键合 (E-M)2 （E = S、Se、Te；R/M = H/1、Me/2、CN/3）进行了气相和二氯甲烷溶液计算。分子静电势表明，E、R 的变化会影响 E-M/(E-M)2 的 σ 孔和 π 孔。远距离 R 通过长程静电场效应起作用。ChB 强度按 S < Se < Te 和 (E-2)2 < (E-1)2 < (E-3)2 的顺序增加。主要的驱动力是静电和分散相互作用。晶体 S-1 和 Se-2 具有头对头二聚体。Se-3 通过 Se-Ncyano ChB 显示头尾链。在设计和合成用于基本原理和应用的新型 E-M/(E-M)2时，应考虑不同 ChB 之间以及 ChB 与其他 SBI 之间的竞争。

{"title":"Influence of 2,1,3-pyrazinochalcogenadiazoles structure on their dimerization via chalcogen bonding (chalcogen = S, Se, Te)","authors":"Qiaoyu Wei , Hui Wang , Andrey V. Zibarev","doi":"10.1016/j.comptc.2024.114984","DOIUrl":"10.1016/j.comptc.2024.114984","url":null,"abstract":"<div><div>Chalcogen bonding (<em>ChB</em>) is an σ-hole-driven secondary bonding interaction (SBI). The crystalline 2,1,3-<em>benzo</em>chalcogenadiazoles involved in organic optoelectronics is exemplified by [E···N]<sub>2</sub> supramolecular synthon. For 5,6- R<sub>2</sub> −2,1,3-<em>pyrazino</em>chalcogenadiazoles E-<strong>M</strong> and [E···N]<sub>2</sub>-bonded (E-<strong>M</strong>)<sub>2</sub> (E = S, Se, Te; R/<strong>M</strong> = H/<strong>1</strong>, Me/<strong>2</strong>, CN/<strong>3</strong>), gas-phase and dichloromethane solution calculations are performed. The molecular electrostatic potential suggests that changes in E, R influence σ- and π-holes of E-<strong>M</strong>/(E-<strong>M</strong>)<sub>2</sub>. Distant R acts via long-range electrostatic field effect. <em>ChB</em> strength increases in the order S < Se < Te, and (E-<strong>2</strong>)<sub>2</sub> < (E-<strong>1</strong>)<sub>2</sub> < (E-<strong>3</strong>)<sub>2</sub>. The main driving forces are electrostatic and dispersion interactions. Crystalline S-<strong>1</strong> and Se-<strong>2</strong> have head-to-head dimers. Se-<strong>3</strong> shows head-to-tail chains via Se···N<sub>cyano</sub> <em>ChB</em>. A competition between different <em>ChB</em>, and, between <em>ChB</em> and other SBIs, should be considered in the design and synthesis of new E-<strong>M</strong>/(E-<strong>M</strong>)<sub>2</sub> for fundamentals and applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114984"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657677","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}

引用次数: 0

Investigation of the adsorption behaviors of novel Au3 cluster decorated arsenene nanosheets towards thiophene and methanethiol detection: A DFT study 新型 Au3 簇装饰砷烯纳米片对噻吩和甲硫醇检测的吸附行为研究：DFT 研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-11-09 DOI: 10.1016/j.comptc.2024.114975

Farag M.A. Altalbawy , Subbulakshmi Ganesan , I.A. Ariffin , Madan Lal , Rajni Verma , Safaa Mohammed Ibrahim , Mustafa Jassim Al-saray , Jaber Hameed Hussain , Mohammed Yaqob , Merwa Alhadrawi

First principles calculations were carried out to describe the interactions between Au_n-arsenene nanosheets and methanethiol/thiophene molecules. Both Au-arsenene and Au₃-arsenene nanosheets exhibit smaller band gap than the pure arsenene system due to the emergence of new energy bands near the Fermi level. Thus, the conductivity and sensor capabilities are significantly enhanced for the Au functionalized arsenene nanosheets. Calculated formation energies of −2.38 eV and −5.37 eV for Au-arsenene and Au₃-arsenene nanosheets indicate their structural stability. The adsorption of methanethiol and thiophene molecules on the Au-arsenene substrates spontaneously occurs due to the negative calculated adsorption energies. Besides, thiophene molecule exhibits the highest adsorption energy (−0.52 eV) on the Au-arsenene substrate through its S atom strongly connected to the Au atom. The moderate adsorption energies indicate the shorter recovery times for sensing applications. Our work sheds light on the exploration of Au-arsenene as an effective candidate for sensing methanethiol and thiophene molecules.

第一性原理计算描述了 Aun-arsenene 纳米片与甲硫醇/噻吩分子之间的相互作用。由于在费米水平附近出现了新的能带，Au-砒霜烯和 Au3-砒霜烯纳米片都显示出比纯砒霜烯系统更小的带隙。因此，金功能化砷烯纳米片的电导率和传感器功能显著增强。Au-arsenene 和 Au3-arsenene 纳米片的计算形成能分别为 -2.38 eV 和 -5.37 eV，这表明它们具有稳定的结构。由于计算得出的吸附能为负值，甲硫醇和噻吩分子会自发地吸附在金-烯烃基底上。此外，噻吩分子通过其与金原子紧密相连的 S 原子在金-烯基底上显示出最高的吸附能（-0.52 eV）。适中的吸附能表明传感应用的恢复时间更短。我们的工作为探索金-烯烃作为传感甲硫醇和噻吩分子的有效候选材料提供了启示。

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