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Min Zhang Yan Li Ze‐Sheng Li Jia‐Zhong Sun 《International journal of quantum chemistry》2010,110(6):1142-1151
The geometries, energies, and electronic properties of a series of phosphorescent Pt(II) complexes including FPt, CFPt, COFPt, and NFPt have been characterized within density functional theory DFT calculations which can reproduce and rationalize experimental results. The properties of excited‐states of the Pt(II) complexes were characterized by configuration interaction with singles (CIS) method. The ground‐ and excited‐state geometries were optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. In addition, we also have performed a triplet UB3LYP optimization for complex FPt and compared it with CIS method in the emission properties. The datum (562.52 nm) of emission wavelength for complex FPt, which were computed based on the triplet UB3LYP optimization excited‐state geometry, is not agreement with the experiment value (500 nm). The absorption and phosphorescence wavelengths were computed based on the optimized ground‐ and excited‐state geometries, respectively, by the time‐dependent density functional theory (TD‐DFT) methods. The results revealed that the nature of the substituent at the phenylpyridine ligand can influence the distributions of HOMO and LUMO and their energies. Moreover, the auxiliary ligand pyridyltetrazole can make the molecular structure present a solid geometry. In addition, the charge transport quality has been estimated approximately by the predicted reorganization energy (λ). Our result also indicates that the substitute groups and different auxiliary ligand not only change the nature of transition but also affect the rate and balance of charge transfer. By summarizing the results, we can conclude that the NFPt is good OLED materials with a solid geometry and a balanced charge transfer rate. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
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Min Zhang Ze‐Sheng Li Yan Li Jia Liu Jia‐Zhong Sun 《International journal of quantum chemistry》2009,109(6):1167-1176
The geometries, spectroscopic and electronic structures properties of a series of heteroleptic phosphorescent Ir(III) complexes including N981, N982, N983, N984 have been characterized by density functional theory calculations. The excited‐state properties of the Ir(III) complexes have been characterized by CIS method. The ground‐ and excited‐state geometries were optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. By using the time‐dependent density functional theory method, the absorption and phosphorescence spectra were calculated based on the optimized ground‐ and excited‐state geometries, respectively. The results show that the absorption and emission data agree well with the corresponding experimental results. The calculated results also revealed that the nature of the substituent at the 4‐position of the pyridyl moiety can influence the distributions of HOMO and LUMO and their energies. In addition, the charge transport quality has been estimated approximately by the calculated reorganization energy (λ). Our result also indicates that the positions of the substitute groups not only change the transition characters but also affect the charge transfer rate and balance, and complex N982 is a very good charge transfer material for green OLEDs. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 相似文献
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Sharmin Akther Rupa Md. Rassel Moni Md. Abdul Majed Patwary Md. Mayez Mahmud Md. Aminul Haque Jamal Uddin S. M. Tareque Abedin 《Molecules (Basel, Switzerland)》2022,27(5)
Polytopic organic ligands with hydrazone moiety are at the forefront of new drug research among many others due to their unique and versatile functionality and ease of strategic ligand design. Quantum chemical calculations of these polyfunctional ligands can be carried out in silico to determine the thermodynamic parameters. In this study two new tritopic dihydrazide ligands, N’2, N’6-bis[(1E)-1-(thiophen-2-yl) ethylidene] pyridine-2,6-dicarbohydrazide (L1) and N’2, N’6-bis[(1E)-1-(1H-pyrrol-2-yl) ethylidene] pyridine-2,6-dicarbohydrazide (L2) were successfully prepared by the condensation reaction of pyridine-2,6-dicarboxylic hydrazide with 2-acetylthiophene and 2-acetylpyrrole. The FT-IR, 1H, and 13C NMR, as well as mass spectra of both L1 and L2, were recorded and analyzed. Quantum chemical calculations were performed at the DFT/B3LYP/cc-pvdz/6-311G+(d,p) level of theory to study the molecular geometry, vibrational frequencies, and thermodynamic properties including changes of ∆H, ∆S, and ∆G for both the ligands. The optimized vibrational frequency and (1H and 13C) NMR obtained by B3LYP/cc-pvdz/6-311G+(d,p) showed good agreement with experimental FT-IR and NMR data. Frontier molecular orbital (FMO) calculations were also conducted to find the HOMO, LUMO, and HOMO–LUMO gaps of the two synthesized compounds. To investigate the biological activities of the ligands, L1 and L2 were tested using in vitro bioassays against some Gram-negative and Gram-positive bacteria and fungus strains. In addition, molecular docking was used to study the molecular behavior of L1 and L2 against tyrosinase from Bacillus megaterium. The outcomes revealed that both L1 and L2 can suppress microbial growth of bacteria and fungi with variable potency. The antibacterial activity results demonstrated the compound L2 to be potentially effective against Bacillus megaterium with inhibition zones of 12 mm while the molecular docking study showed the binding energies for L1 and L2 to be −7.7 and −8.8 kcal mol−1, respectively, with tyrosinase from Bacillus megaterium. 相似文献
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苯并咪唑及其衍生物具有良好的生物活性和荧光性质[1,2],在DNA拓扑酶抑制剂、HIV逆转录酶的抑制剂、分子探针等领域已有广泛应用,一直以来都是广大学者研究的热点[3]。苯并咪唑类化合物是一类活性很强的内吸型杀菌剂,它的主要作用方式是植物病原的R-微管蛋白结合,破坏R-微管蛋白的功能,抑制真菌的有丝分裂和形态建构。然而,随着使用时间的增加,病菌的抗生越来越强,导致在部分地区失效,给农业生产带来巨大损失。所以迫切需要寻找高效、新型的杀菌剂。近些年来,二茂铁衍生物因其广泛的生物活性,如抗癌、杀菌、杀虫、抗炎及调节植物生长等… 相似文献
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Innocent Benjamin Hitler Louis Akaninyene D. Udoikono Ernest C. Agwamba Tomsmith O. Unimuke Eze F. Ahuekwe 《Vietnam Journal of Chemistry》2023,61(1):109-125
In this study, two derivatives of hydrazineylidene-3-oxopropanal: chlorophenyl (CPHO) and Nitrophenyl (NPHO) substituted hydrazineylidene compounds were synthesized, spectroscopically characterized using (FT-IR, UV, and NMR), and theoretically modelled as a potential drug for the treatment of antiviral hepatitis (HBV and HCV) using in-sillico molecular docking approach. Electronic structure investigation based on density functional theory (DFT) at the B3LYP/6-311++G(d,p) level of theory was conducted for the investigation of the structural, reactivities, and electronic properties of the studied compounds. The FT-IR analysis in gas, water, ethanol and DMSO indicates a maximum stretching vibrations frequencies of C-H in NPHO between 3249.38 to 3254.77 cm-1 and 3236.04 to 3240.66 cm-1 for CPHO, N-H for NPHO is 3309.81 to 3336.37 cm-1, and CPHO is 3330.11 to 3331.18 cm-1, C=O in NPHO to be 1685.55 to 1705.60 cm-1, and 1700.31 to 1679.15 cm-1 for CPHO. The C-N stretching vibrations in NPHO were 1519.98 to 1562.06 cm-1 and 1430.05 to 1460.33 cm-1 for CPHO. The UV-Vis analysis indicates that NPHO wavelength absorption spectrum showed high excitation energy bands between 369.74 to 440.60 nm and CPHO at 178.95 to 434.08 nm. The highest stabilization energy of NPHO is LP (1) N12 donor and LP*(1) H10 acceptor with a value of 417.54 kcal/mol compared to πC17 - O18 donor and π*C19 - C28 acceptor with a value of 108.33 kcal/mol for CPHO. The molecular binding affinity of CPHO and NPHO had a high mean binding affinity of -5.83 and -6.05 kcal/mol, compared to the standard antiviral drugs with -5.00 kcal/mol. Therefore, the compounds show excellent reactivity based on the electronic structure, spectroscopic characterization and represent a potential antiviral agent treatment for HBV and HCV. 相似文献
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Anoop Kumar Pandey S.P. Pandey V.K. Singh Vijay Narayan Dharmesh Vikram Shukla Vijay Singh Apoorva Dwivedi 《Macromolecular Symposia》2024,413(1):2300076
In this paper, a complete quantum chemical study of propofol molecule has been done by using DFT-B3LYP/6-311G (d, p) method. The equilibrium geometry, HOMO–LUMO gap, NBO calculation, and DOS have been studied with the help of density functional theory (DFT) employing 6–311G (d, p) as the basis set. A good correlation is observed between experimental and calculated vibrational frequencies. Its molecular docking with 1B4N receptor shows that propofol can bind and inhibit the receptor enzymes therefore can act as an effective drug. NLO calculation shows that the molecule is good non-linear optical candidate in future due to its more ICT moment of π–electron. Study shows that title molecule binds well with 1B4N protein. 相似文献
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用从头计算分子轨道法和密度泛函理论 ,在HF/6 31G 和B3LYP/6 31G 水平上对ClnAlNHn 和HnAlNHn(n =1～ 3)及其碎片分子的几何构型、电子结构、振动光谱和化学热力学性质进行了理论研究。结果表明 ,优化几何参数与实验值相吻合。Cl2 AlNH2 和H2 AlNH2 分子中 ,Al-N键为由一个σ键和一个π键组成的双重键 ,旋转势垒分别为 34.10和 5 4 .35kJ·mol- 1。而Cl3AlNH3和H3AlNH3分子中 ,Al-N键为σ型单键 ,对应的旋转势垒为 0 .31和 2 .5 0kJ·mol- 1,有较小的势垒 ,易于旋转。化学热力学计算表明 ,ClnAlNHn 和HnAlNHn 分子中 ,Al-N键能的大小顺序为△Hn =2>△Hn =1>△Hn =3. 相似文献
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In this work, density functional theory (DFT) and time‐dependent DFT (TDDFT) methods were used to investigate the excited‐state dynamics of the excited‐state hydrogen‐bonding variations and proton transfer mechanism for a novel white‐light fluorophore 2‐(4‐[dimethylamino]phenyl)‐7‐hyroxy‐6‐(3‐phenylpropanoyl)‐4H‐chromen‐4‐one ( 1 ). The methods we adopted could successfully reproduce the experimental electronic spectra, which shows the appropriateness of the theoretical level in this work. Using molecular electrostatic potential (MEP) as well as the reduced density gradient (RDG) versus the product of the sign of the second largest eigenvalue of the electron density Hessian matrix and electron density (sign[λ2]ρ), we demonstrate that an intramolecular hydrogen bond O1–H2···O3 should be formed spontaneously in the S0 state. By analyzing the chemical structures, infrared vibrational spectra, and hydrogen‐bonding energies, we confirm that O1–H2·O3 should be strengthened in the S1 state, which reveals the possibility of an excited‐state intramolecular proton transfer (ESIPT) process. On investigating the excitation process, we find the S0 → S1 transition corresponding to the charge transfer, which provides the driving force for ESIPT. By constructing the potential energy curves, we show that the ESIPT reaction results in a dynamic equilibrium in the S1 state between the forward and backward processes, which facilitates the emission of white light. 相似文献
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2-氟-5-溴吡啶分子振动光谱的密度泛涵理论研究 总被引：2，自引：1，他引：2
用密度泛函理论方法B3LYP以及6-311++G(2df,2pd)基组对2-氟-5-溴吡啶分子 的平衡几何构型进行了优化并计算了该分子的振动谐力场。使用Pulay的标度方法 对理论力场进行了标度。采用Wilson的GF矩阵方法,根据标度后的理论力场进行了 简正坐标分析,对2-氟-5-溴吡啶分子的振动基频进行了理论研究,得到了势能分 布和红外振动频率。与红外频率的实验值相比较,理论频率的均方差为24 cm~(-1) 。此外,根据振动模式的势能分布对此分子的振动基频进行了理论归属,并对前人 的指认进行了修正和补充。 相似文献
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The level of selenocysteine (Sec) in the human body is closely related to a variety of pathophysiological states, so it is important to study its fluorescence sensing mechanism for designing efficient fluorescent probes. Herein, we used time-dependent density functional theory to investigate the fluorescence sensing mechanism of phenanthroimidazole derivates A4 and B4 for the detection of Sec, which are proposed to be designed based on excited state intramolecular proton transfer (ESIPT) and intramolecular charge transfer (ICT) mechanisms. The calculation results show that the fluorescence quenching mechanism of A4 and B4 is due to the photo-induced electron transfer (PET) process with the sulfonate group acts as the electron acceptor. Subsequently, A4 and B4 react with Sec, the sulfonate group is substituted by hydroxyl groups, PET is turned off, and significant fluorescence enhancement of the formed A3 and B3 is observed. The theoretical results suggest that the fluorescence enhancement mechanism of B3 is not based on ICT mechanism, and the charge transfer phenomenon was not observed by calculating the frontier molecular orbitals, and proved to be a local excitation mode. The reason for the fluorescence enhancement of A3 based on ESIPT is also explained by the calculated potential energy curves. 相似文献
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用多种密度泛函理论(DFT)方法(BLYP/6-31G^*^*,B3LYP/6-31G^*^*,B3PW91/6-31G^*^*和SVWN/6-31G^*^*)对吲哚分子的平衡几何构型进行了优化。在优化构型的基础上计算了吲哚分子的谐力场、振动基频和红外光谱强度。计算得到的振动频率与实验值比较平均偏差对四种计算方法(BLYP/6-31G^*^*,P3LYP/6-31G^*^*,B3PW91/6-31G^*^*和SVWN/6-31G^*^*)分别为16.3,40.5,45.1和26.4cm^-^1。BLYP/6-31G^*^*理论力场被用于吲哚分子的简正坐标分析计算中。根据振动率的势能分布(PEDs)对此分子的振动基频进行了理论归属。 相似文献
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The title compound, 1-(naphthalene-2-yl)-2-(1H-pyrazol-1-yl)ethanone O-butyl oxime, I, was synthesized. The crystal and molecular structures of I were determined by IR, 1H-NMR, mass spectrum, elemental analysis and X-ray single crystal diffraction. Molecular geometry from X-ray experiment of I in the ground state was compared using the Density Functional Theory (DFT) with B3LYP/6-311G(d,p) basis set. In addition, DFT calculation, molecular electrostatic potentials (MEP) and frontier molecular orbitals of I were performed at the B3LYP/6-311G(d,p) level of the theory. 相似文献
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Dr. Yuta Tsuji Prof. Dr. Roald Hoffmann 《Angewandte Chemie (International ed. in English)》2014,53(16):4093-4097
For transmission of electrons through a π system, when the Landauer theory of molecular conductance is viewed from a molecular orbital (MO) perspective, there obtains a simple perturbation theoretic dependence, due to Yoshizawa and Tada, on a) the product of the orbital coefficients at the sites of electrode attachment, and b) the MO energies. The frontier orbitals consistently and simply indicate high or low transmission, even if other orbitals may contribute. This formalism, with its consequent reinforcement and/or interference of conductance, accounts for the (previously explained) difference in direct vs. cross conjugated transmission across an ethylene, as well as the comparative ON/OFF ratios in the experimentally investigated dimethyldihydropyrene and dithienylethene‐type single‐molecule switches. A strong dependence of the conductance on the site of attachment of the electrodes in a π system is an immediate extrapolation; the theory then predicts that for some specified sites the switching behavior will be inverted; i.e. the “open” molecular form of the switch will be more conductive. 相似文献
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S. A. Siddiqui A. Dwivedi P. K. Singh T. Hasan S. Jain O. Prasad N. Misra 《Journal of Structural Chemistry》2009,50(3):411-420
This work is devoted to theoretical study on molecular structure of protopine. The equilibrium geometry, harmonic vibrational frequencies and infrared intensities were calculated by ab initio Hartree-Fock and density functional B3LYP methods with the 6-31G(d) basis set and were interpreted in terms of potential energy distribution (PED) analysis. The internal coordinates were optimized repeatedly for many times to maximize the PED contributions. A detailed interpretation of the infrared spectra of protopine is reported. The calculations are in agreement with experiment. The thermodynamic functions of the title compound were also performed at HF/6-31G(d) and B3LYP/6-31G(d) level of theory. The FT-IR spectra of protopine were recorded in solid phase. 相似文献
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The MM4 force field has been extended to the title class of compounds. The vibrational spectra, structures, conformational equilibria, and heats of formation have been studied for 47 conformers of 29 compounds. In general, the properties may be calculated with accuracy that is competitive with that for hydrocarbons. The structures are better fit than previously because of the inclusion of a torsion–bend interaction term, which has its origin in the lone pair (Bohlmann) effect. Available experimental data do not suffice to yield detailed torsional potentials, or geometries as a function of torsion angle, and these quantities were determined by ab initio calculations at the MP2/6-31G* level. The rms error in the calculated frequencies of seven representative structures (with a total of 64 experimental and 96 ab initio frequencies) is 25 cm−1. The heats of formation for 23 compounds have a weighted rms error of 0.36 kcal/mol. © 1997 John Wiley & Sons, Inc. J Comput Chem 18 : 1827–1847, 1997 相似文献
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实验研究结果表明双核金属酞菁类化合物ＭＰｃ－ＰｃＭ（Ｍ＝Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ）是催化Ｈ＿２Ｓ液相氧化反应的良好催化剂，且其催化活性顺序为Ｃｏ＞Ｎｉ＞Ｖ＞Ｆｅ＞Ｃｕ＞Ｃｒ＞Ｍｎ．采用量子化学理论计算方法（ＩＮＤＯ／Ｓ）分析了其前线分子轨道的构成特征，结果表明这几种ＭＰｃ－ＰｃＭ的ＬＵＭＯ轨道皆为有金属离子参与形成的π轨道，但ＨＯＭＯ轨道间的差异却很大．Ｍ＝Ｃｏ、Ｎｉ、Ｃｕ、Ｃｒ时，其ＨＯＭＯ为π轨道；而Ｍ＝Ｆｅ、Ｍｎ时，其ＨＯＭＯ却为σ轨道．正是在前线分子轨道的轨道类型、共轭程度及金属轨道贡献三方面因素的协同作用下，才导致ＭＰｃ－ＰｃＭ的催化活性顺序并非按中心金属离子价电子层ｄ电子数的递变而呈现出规律性的变化． 相似文献