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1.
《Arabian Journal of Chemistry》2022,15(3):103673
In this study, we designed a series of pyrene-based donor-π-donor-π-acceptor compounds (HPTC1-HPTC7) by structural tailoring the reference compound (HPTC) using acceptor units. Nonlinear optical (NLO) properties, frontier molecular orbitals (FMOs), natural bonding orbital (NBO), transition density matric (TDM) analysis, and absorption spectra of reference and proposed derivatives were calculated at M06/6-31G(d,p) functional. All the designed compounds have smaller energy bandgaps than the HPTC compound. Moreover, the designed compounds exhibited larger global softness values than the reference. The absorption maxima of HPTC2, HPTC3, and HPTC7 are blue shifted with respect to HPTC. NBO analysis revealed that prolonged hyper conjugative associations and strong interactions between the donor (π) and acceptor (π*) moieties play a crucial part in their stabilization. The FMO and NBO findings supported the NLO responses of entitled compounds, and consequently, the linear and nonlinear properties of designed derivatives elevate compared to the reference molecule. Promisingly, the NLO response for HPTC7 comprises of highest values of <α>, βtotal and < γ > as 1.92 × 10?22 esu, 1.95 × 10?27 esu, and 4.69 × 107 (a.u). This NLO behavior shows push–pull NLO chromophores for HPTC7 predicting its role in pursuing NLO materials for optoelectronic applications. 相似文献
2.
Rita Kakkar Mallika Pathak Preeti Chadha 《International journal of quantum chemistry》2005,102(2):189-199
The rearrangement of vinylidene to acetylene has been studied in detail by the density functional method, using Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Parr. The rearrangement of the anion, as well as that of fluoro‐substituted systems, has also been investigated, in order to determine the effect of fluorine substitution on the activation barrier to the 1,2‐hydrogen shift, as well as the relative migratory aptitudes of hydrogen and fluorine. Natural bond orbital analysis is invoked to gain insight into the mechanisms of the rearrangements. Basis size effects are also discussed, particularly in relation to anionic systems. The need to include diffuse functions in geometry optimizations of anionic systems is reinforced by the present calculations. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
3.
The complexes between R3Tr (Tr = B, Al, and Ga; R = H, F, Cl, and Br) and H2X (X = O, S, and Se) were theoretically studied. The interaction energies of R3Al⋯H2X and R3Ga⋯H2X are consistent with the electronegativity of the halogen atom R (R ≠ H), but an opposite dependence is found for R3B⋯H2X. The triel bond of R3Tr⋯H2X is weaker for the heavier chalcogen donor. The dependence of triel bonding strength on the triel atom is complicated, depending on the nature of R and X. The methyl substitution of H2X causes a substantial increase in the interaction energy from −5.74 kcal/mol to −22.88 kcal/mol, and its effect is relevant to the nature of Tr, X, and R groups. For the S and Se donors, the increased percentage of interaction energy is almost the same due to the methyl substitution, which is larger than that of the O analogue. In most triel-bonded complexes, electrostatic dominates and polarization has comparable contribution. However, polarization plays a dominant role in R3B⋯ and R3B⋯ (R = Cl and Br; R′ = H and Me). 相似文献
4.
Complete geometry optimizations were carried out by HF and DFT methods to study the molecular structure of binuclear transition-metal compounds (Cp(CO)3W(μ-PPh2)W(CO)5) (I) and (Cp(CO)2W(μ-PPh2)W(CO)5) (II). A comparison of the experimental data and calculated structural parameters demonstrates that the most accurate geometry parameters are predicted by the MPW1PW91/LANL2DZ among the three DFT methods. Topological properties of molecular charge distributions were analyzed with the theory of atoms in molecules. (3, −1) critical points, namely bond critical point, were found between the two tungsten atoms, and between W1 and C10 in complex II, which confirms the existence of the metal–metal bond and a semi-bridging CO between the two tungsten atoms. The result provided a theoretical guidance of detailed study on the binuclear phosphido-bridged complex containing transition metal–metal bond, which could be useful in the further study of the heterobimetallic phosphido-bridged complexes. 相似文献
5.
6.
Michelle Bitencourt Matheus P. Freitas Roberto Rittner 《Journal of Molecular Structure》2007,840(1-3):133-136
The effect of attaching an additional fluorine atom at C-2 in 1-fluoropropane (FP), giving 1,2-difluoropropane (DFP), on its conformational equilibrium, is theoretically evaluated. This substitution causes critical implications on the conformer stabilities of DFP (TG, GT and GG conformations) and the steric and electrostatic interactions should favor the conformer with fluorine atoms trans. However, the gauche effect plays a major role in describing the energies balance in DFP, shifting the equilibrium towards the conformation in which the two fluorine atoms are gauche. The origin of this effect is discussed through an NBO analysis, which allows the evaluation of both classical and non-classical (hyperconjugation and bent bonds) interactions as the prevailing factors governing the conformational equilibrium of molecules containing the 1,2-difluoroethane fragment. 相似文献
7.
The restricted rotation about the partial C,N double bond in 2-chloro-6-NR2-pyran-4-ones is discussed in the light of NMR spectroscopic data and theoretical calculations.Ab initio calculations at the HF/6-31G* level were carried out using a continuum model to take solvent effects into account. The delocalization of-electron density [described by natural bond orbital analysis (NBO)] was applied to determine the degree of conjugation in the ground state (GS) and in the transition state (TS) for the restricted rotation of the compounds studied. The reason for the different barriers to rotation of the NR2 substituents (pyrrolidino > dimethylamino > morpholidino > piperidino) at the 2-chloro-pyran-4-one ring appears to be the different steric hindrance of the NR2 substituents in the GS for the restricted rotation. 相似文献
8.
Methyl radical complexes H3C…HCN and H3C…HNC have been investigated at the UMP2(full)/aug‐cc‐pVTZ level to elucidate the nature of hydrogen bonds. To better understand the intermolecular H‐bond interactions, topological analysis of electron density at bond critical points (BCP) is executed using Bader's atoms‐in‐molecules (AIM) theory. Natural bond orbital (NBO) analysis has also been performed to study the orbital interactions and change of hybridization. Theoretical calculations show that there is no essential difference between the blue‐shift H‐bond and the conventional one. In H3C…HNC complex, rehybridization is responsible for shortening of the N? H bond. The hyperconjugative interaction between the single electron of the methyl radical and N? H antibonding orbital is up to 7.0 kcal/mol, exceeding 3.0 kcal/mol, the upper limit of hyperconjugative n(Y)→σ*(X–H) interaction to form the blue‐shifted H‐bond according to Alabugin's theory. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
9.
In order to study the effects of R group on Fe–Hg interactions and 31P chemical shifts, the structures of mononuclear complexes Fe(CO)3(PPh2R)2 (R=pym:1, fur: 2, py: 3,thi: 4; pym=pyrimidine, fur=furyl, py=pyridine, thi=thiazole) and binuclear complexes [Fe(CO)3(PPh2R)2(HgCl2)] (R=pym: 5, fur: 6, py: 7, thi: 8) were studied using the density functional theory (DFT) PBE0 method. The 31P chemical shifts were calculated by PBE0-GIAO method. Nature bond orbital (NBO) analyses were also performed to explain the nature of the Fe–Hg interactions. The conclusions can be drawn as follows: (1) The complexes with nitrogen donor atoms are more stable than those with O or S atoms. The more N atoms there are, the higher is the stabilility of the complex. (2) The Fe–Hg interactions play a dominant role in the stabilities of the complexes. In 5 or 6, thereisa σ-bond between Fe and Hg atoms. However, in 7 and 8, the Fe–Hg interactions act as σP–Fe→nHg and σC–Fe→nHg delocalization. (3) Through Fe→Hg interactions, there is charge transfer from R groups towards the P, Fe, and Hg atoms, which increases the electron density on P nucleus in binuclear complexes. As a result, compared with their mononuclear complexes, the 31P chemical shifts in binuclear complexes show some reduction. 相似文献
10.
运用密度泛函PBE0方法研究了双核金属茂合物Zn2(η5-E5)2(E=N, P, As, Sb)的电子结构, 运用自然键轨道(NBO)方法对该体系的电荷分布及成键特征进行了分析. 此类体系中存在Zn—Zn的σ单键, 为近似纯s成分的成键方式. 用含时密度泛函理论(TDDFT ) 完全态求和(SOS) 方法计算了该体系的三阶非线性光学系数, 结果表明, γ值与最大吸收波长λmax成正比, 在各个分量中, 对〈γ〉起主要贡献的是γzzzz, 最大吸收波长对应的电子跃迁是从Zn—Zn的σ成键轨道到Zn—Zn的σ*反键轨道. 相似文献