scholarly journals Charge Transfer Complexes of 1,3,6-Trinitro-9,10-phenanthrenequinone with Polycyclic Aromatic Compounds

Molecules ◽  
2021 ◽  
Vol 26 (21) ◽  
pp. 6391
Author(s):  
Roman Linko ◽  
Michael Ryabov ◽  
Pavel Strashnov ◽  
Pavel Dorovatovskii ◽  
Victor Khrustalev ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Density Functional ◽  
Energy Levels ◽  
Orbital Energy ◽  
Charge Transfer Complexes ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
Donor And Acceptor ◽  
Polycyclic Aromatic ◽  
And Control

Understanding the interactions of organic donor and acceptor molecules in binary associates is crucial for design and control of their functions. Herein, we carried out a theoretical study on the properties of charge transfer complexes of 1,3,6-trinitro-9,10-phenanthrenequinone (PQ) with 23 aromatic π-electron donors. Density functional theory (DFT) was employed to obtain geometries, frontier orbital energy levels and amounts of charge transfer in the ground and first excited states. For the most effective donors, namely, dibenzotetrathiafulvalene, pentacene, tetrathiafulvalene, 5,10-dimethylphenazine, and tetramethyl-p-phenylenediamine, the amount of charge transfer in the ground state was shown to be 0.134−0.240 e−. Further, a novel charge transfer complex of PQ with anthracene was isolated in crystalline form and its molecular and crystal structure elucidated by single-crystal synchrotron X-ray diffraction.

On the Nature of Halide-Water Interactions: Insights from Many-Body Representations and Density Functional Theory

2019 ◽  
Author(s):  
Brandon B. Bizzarro ◽  
Colin K. Egan ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Molecular Orbital ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Orbital Energy ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory

<div> <div> <div> <p>Interaction energies of halide-water dimers, X<sup>-</sup>(H<sub>2</sub>O), and trimers, X<sup>-</sup>(H<sub>2</sub>O)<sub>2</sub>, with X = F, Cl, Br, and I, are investigated using various many-body models and exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. Analysis of the results obtained with the many-body models demonstrates the need to capture important short-range interactions in the regime of large inter-molecular orbital overlap, such as charge transfer and charge penetration. Failure to reproduce these effects can lead to large deviations relative to reference data calculated at the coupled cluster level of theory. Decompositions of interaction energies carried out with the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method demonstrate that permanent and inductive electrostatic energies are accurately reproduced by all classes of XC functionals (from generalized gradient corrected (GGA) to hybrid and range-separated functionals), while significant variance is found for charge transfer energies predicted by different XC functionals. Since GGA and hybrid XC functionals predict the most and least attractive charge transfer energies, respectively, the large variance is likely due to the delocalization error. In this scenario, the hybrid XC functionals are then expected to provide the most accurate charge transfer energies. The sum of Pauli repulsion and dispersion energies are the most varied among the XC functionals, but it is found that a correspondence between the interaction energy and the ALMO EDA total frozen energy may be used to determine accurate estimates for these contributions. </p> </div> </div> </div>

Binding Energies of Organic Charge-Transfer Complexes Calculated by First-Principles Methods

1998 ◽  
Vol 63 (8) ◽  
pp. 1223-1244 ◽  
Author(s):  
Cordula Rauwolf ◽  
Achim Mehlhorn ◽  
Jürgen Fabian
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Ground State ◽  
Density Functional ◽  
Binding Energies ◽  
Basis Set ◽  
Dispersion Energy ◽  
Functional Theory ◽  
Basis Set Superposition Error ◽  
Donor And Acceptor

Weak interactions between organic donor and acceptor molecules resulting in cofacially-stacked aggregates ("CT complexes") were studied by second-order many-body perturbation theory (MP2) and by gradient-corrected hybrid Hartree-Fock/density functional theory (B3LYP exchange-correlation functional). The complexes consist of tetrathiafulvalene (TTF) and related compounds and tetracyanoethylene (TCNE). Density functional theory (DFT) and MP2 molecular equilibrium geometries of the component structures are calculated by means of 6-31G*, 6-31G*(0.25), 6-31++G**, 6-31++G(3df,2p) and 6-311G** basis sets. Reliable molecular geometries are obtained for the donor and acceptor compounds considered. The geometries of the compounds were kept frozen in optimizing aggregate structures with respect to the intermolecular distance. The basis set superposition error (BSSE) was considered (counterpoise correction). According to the DFT and MP2 calculations laterally-displaced stacks are more stable than vertical stacks. The charge transfer from the donor to the acceptor is small in the ground state of the isolated complexes. The cp-corrected binding energies of TTF/TCNE amount to -1.7 and -6.3 kcal/mol at the DFT(B3LYP) and MP2(frozen) level of theory, respectively (6-31G* basis set). Larger binding energies were obtained by Hobza's 6-31G*(0.25) basis set. The larger MP2 binding energies suggest that the dispersion energy is underestimated or not considered by the B3LYP functional. The energy increases when S in TTF/TCNE is replaced by O or NH but decreases with substitution by Se. The charge-transferred complexes in the triplet state are favored in the vertical arrangement. Self-consistent-reaction-field (SCRF) calculations predicted a gain in binding energy with solvation for the ground-state complex. The ground-state charge transfer between the components is increased up to 0.8 e in polar solvents.

Cross-conjugation as a Motif for Organic Non-Linear Optical Molecules

2014 ◽  
Vol 1698 ◽  
Author(s):  
Meghana Rawal ◽  
Kerry Garrett ◽  
Andreas F. Tillack ◽  
Werner Kaminsky ◽  
Evgheni Jucov ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Dipole Moments ◽  
X Ray Diffraction ◽  
Conjugated Molecules ◽  
Functional Theory ◽  
Highest Occupied Molecular Orbital ◽  
Donor And Acceptor ◽  
Vis Spectroscopy ◽  
Lowest Unoccupied Molecular Orbital

ABSTRACTWe studied the effect of a cross-conjugated bridging group (χC) on charge-transfer in a push-pull chromophore system. The hyperpolarizability of such molecules was found to be comparable to that of a fully π-conjugated molecule (πC) with the same donor and acceptor. The cross-conjugated moiety was then applied as a pendant to a fully π-conjugated chromophore containing a tricyanopyrroline acceptor (TCP). The addition of a χC moiety did not alter the intrinsic hyperpolarizability and provides an avenue for extending and aiding πC systems. The molecules were examined by X-ray diffraction (XRD), hyper-Raleigh scattering (HRS) and UV-visible (UV-vis) spectroscopy. Experimental results were compared with the predictions of density functional theory (DFT). Cross-conjugated molecules have comparable β values, relative to πC molecules, due to reduced spatial overlap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). Thus, the χC architecture could facilitate independent modification of donor and acceptor strengths while minimizing unfavorable effects on electronic transitions and dipole moments.

Design and characteration of planar star-shaped oligomer electron donors for organic solar cells: a DFT study

2015 ◽  
Vol 93 (11) ◽  
pp. 1181-1190 ◽  
Author(s):  
Dongmei Wang ◽  
Zhiyuan Geng
Keyword(s):  
Density Functional Theory ◽  
Solar Cells ◽  
Charge Transfer ◽  
Energy Level ◽  
Organic Solar Cells ◽  
Density Functional ◽  
Short Circuit ◽  
Frontier Molecular Orbital ◽  
Orbital Energy ◽  
Functional Theory

To seek high-performance oligomer donor materials used in organic solar cells, four star-shaped molecules with a planar donor core derived from the recent reported molecule 3T-P-DPP (phenyl-1,3,5-trithienyl-diketopyrrolopyrrole) were designed. The molecular properties affecting the cell performance, such as structural characteristics, frontier molecular orbital energy level, absorption spectra, exciton character, and charge transfer/transport, were investigated by means of the density functional theory and time-dependent density functional theory methods. Comparative analysis showed that the new designed molecule 3 with a TTT (2,4,6-tri(thiophen-2-yl)-1,3,5-triazine) core has better planarity, a lower HOMO energy level, and a higher absorption efficiency, as well as more favorable exciton dissociation and charge transfer than the others, potentially improving the open-circuit voltage and short-circuit current density. Consequently, 3 maybe superior to 3T-P-DPP and may act as a promising donor material candidate for organic solar cells.

scholarly journals Encapsulation and Adsorption of Halogens into Single-Walled Carbon Nanotubes

Micro ◽  
2021 ◽  
Vol 1 (1) ◽  
pp. 140-150
Author(s):  
Navaratnarajah Kuganathan ◽  
Sashikesh Ganeshalingam
Keyword(s):  
Carbon Nanotubes ◽  
Charge Transfer ◽  
Density Functional ◽  
Diatomic Molecules ◽  
Single Walled Carbon Nanotubes ◽  
Charge Transfer Complexes ◽  
Functional Theory ◽  
Single Walled Carbon ◽  
The Stability ◽  
Walled Carbon Nanotubes

Functionalisation of single-walled carbon nanotubes (SWNTs) with atoms and molecules has the potential to prepare charge–transfer complexes for numerous applications. Here, we used density functional theory with dispersion correction (DFT + D) to examine the encapsulation and adsorption efficacy of single-walled carbon nanotubes to trap halogens. Our calculations show that encapsulation is exoergic with respect to gas-phase atoms. The stability of atoms inside SWNTs is revealed by the charge transfer between nanotubes and halogens. Encapsulation of halogens in the form of diatomic molecules is favourable with respect to both atoms and diatomic molecules as reference states. The adsorption of halogens on the outer surfaces of SWNTs is also exothermic. In all cases, the degree of encapsulation, adsorption, and charge transfer is reflected by the electronegativity of halogens.

On the Nature of Halide-Water Interactions: Insights from Many-Body Representations and Density Functional Theory

2019 ◽  
Author(s):  
Brandon B. Bizzarro ◽  
Colin K. Egan ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Molecular Orbital ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Orbital Energy ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory

<div> <div> <div> <p>Interaction energies of halide-water dimers, X<sup>-</sup>(H<sub>2</sub>O), and trimers, X<sup>-</sup>(H<sub>2</sub>O)<sub>2</sub>, with X = F, Cl, Br, and I, are investigated using various many-body models and exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. Analysis of the results obtained with the many-body models demonstrates the need to capture important short-range interactions in the regime of large inter-molecular orbital overlap, such as charge transfer and charge penetration. Failure to reproduce these effects can lead to large deviations relative to reference data calculated at the coupled cluster level of theory. Decompositions of interaction energies carried out with the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method demonstrate that permanent and inductive electrostatic energies are accurately reproduced by all classes of XC functionals (from generalized gradient corrected (GGA) to hybrid and range-separated functionals), while significant variance is found for charge transfer energies predicted by different XC functionals. Since GGA and hybrid XC functionals predict the most and least attractive charge transfer energies, respectively, the large variance is likely due to the delocalization error. In this scenario, the hybrid XC functionals are then expected to provide the most accurate charge transfer energies. The sum of Pauli repulsion and dispersion energies are the most varied among the XC functionals, but it is found that a correspondence between the interaction energy and the ALMO EDA total frozen energy may be used to determine accurate estimates for these contributions. </p> </div> </div> </div>

A new phosphorescent heteroleptic cuprous complex with a neutral 2-methylquinolin-8-ol ligand: synthesis, structure characterization, properties and TD–DFT calculations

2017 ◽  
Vol 73 (6) ◽  
pp. 486-491 ◽  
Author(s):  
Rong-Er Shou ◽  
Li Song ◽  
Wen-Xiang Chai ◽  
Lai-Shun Qin ◽  
Tian-Gen Wang
Keyword(s):  
Charge Transfer ◽  
Density Functional ◽  
Low Cost ◽  
Structure Characterization ◽  
Yellow Emission ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
Ligand Charge Transfer ◽  
Td Dft ◽  
Cuprous Complex

Luminescent CuI complexes have emerged as promising substitutes for phosphorescent emitters based on Ir, Pt and Os due to their abundance and low cost. The title heteroleptic cuprous complex, [9,9-dimethyl-4,5-bis(diphenylphosphanyl)-9H-xanthene-κ2 P,P](2-methylquinolin-8-ol-κ2 N,O)copper(I) hexafluorophosphate, [Cu(C10H9NO)(C39H32OP2)]PF6, conventionally abbreviated as [Cu(Xantphos)(8-HOXQ)]PF6, where Xantphos is the chelating diphosphine ligand 9,9-dimethyl-4,5-bis(diphenylphosphanyl)-9H-xanthene and 8-HOXQ is the N,O-chelating ligand 2-methylquinolin-8-ol that remains protonated at the hydroxy O atom, is described. In this complex, the asymmetric unit consists of a hexafluorophosphate anion and a whole mononuclear cation, where the CuI atom is coordinated by two P atoms from the Xantphos ligand and by the N and O atoms from the 8-HOXQ ligand, giving rise to a tetrahedral CuP2NO coordination geometry. The electronic absorption and photoluminescence properties of this complex have been studied on as-synthesized samples, whose purity had been determined by powder X-ray diffraction. In the detailed TD–DFT (time-dependent density functional theory) studies, the yellow emission appears to be derived from the inter-ligand charge transfer and metal-to-ligand charge transfer (M+L′)→LCT excited state (LCT is ligand charge transfer).

scholarly journals Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates

Symmetry ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1636
Author(s):  
Emna Rtibi ◽  
Benoit Champagne
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Density Functional ◽  
Energy Charge ◽  
Substitution Effects ◽  
First Hyperpolarizability ◽  
Functional Theory ◽  
State Approximation ◽  
Donor And Acceptor

Density functional theory and time-dependent density functional theory have been enacted to investigate the effects of donor and acceptor on the first hyperpolarizability of Lindquist-type organo-imido polyoxometalates (POMs). These calculations employ a range-separated hybrid exchange-correlation functional (ωB97X-D), account for solvent effects using the implicit polarizable continuum model, and analyze the first hyperpolarizabilities by using the two-state approximation. They highlight the beneficial role of strong donors as well as of π-conjugated spacers (CH=CH rather than C≡C) on the first hyperpolarizabilities. Analysis based on the unit sphere representation confirms the one-dimensional push-pull π-conjugated character of the POMs substituted by donor groups and the corresponding value of the depolarization ratios close to 5. Furthermore, the use of the two-state approximation is demonstrated to be suitable for explaining the origin of the variations of the first hyperpolarizabilities as a function of the characteristics of a unique low-energy charge-transfer excited state and to attribute most of the first hyperpolarizability changes to the difference of dipole moment between the ground and that charge-transfer excited state.

DFT investigation on organic dyes with cross-conjugated cyano groups

2014 ◽  
Vol 13 (01) ◽  
pp. 1450008
Author(s):  
Chunhe Yang ◽  
Aiwei Tang ◽  
Fujun Zhang ◽  
Feng Teng
Keyword(s):  
Density Functional ◽  
Molecular Conformation ◽  
Organic Dyes ◽  
Cyano Group ◽  
Energy Levels ◽  
Orbital Energy ◽  
Dye Molecules ◽  
Conjugated Molecules ◽  
Functional Theory ◽  
Cyano Groups

Organic dye molecules with the acceptor moieties, cyano groups, cross-conjugated to the donor moieties, have been investigated theoretically. Density functional theory (DFT) calculations on such cross-conjugated molecules reveal the effects of cross-conjugation on the geometric and electronic structures of the molecules. The cross-conjugated cyano groups in the dye molecules are found effective to alter the charge population and the frontier orbital energy levels of the dyes. The effects of cross-conjugation of cyano group on the molecular conformation, the charge transfer, and polarity of the dyes are discussed.

scholarly journals Simulation Study of Surface Transfer Doping of Hydrogenated Diamond by MoO3 and V2O5 Metal Oxides

Micromachines ◽  
2020 ◽  
Vol 11 (4) ◽  
pp. 433 ◽  
Author(s):  
Joseph McGhee ◽  
Vihar P. Georgiev
Keyword(s):  
Charge Transfer ◽  
Metal Oxides ◽  
Density Functional ◽  
Energy Levels ◽  
Dft Method ◽  
Functional Theory ◽  
Empirical Density ◽  
P Type ◽  
Semi Empirical ◽  
Enhanced Surface

In this work, we investigate the surface transfer doping process that is induced between hydrogen-terminated (100) diamond and the metal oxides, MoO3 and V2O5, through simulation using a semi-empirical Density Functional Theory (DFT) method. DFT was used to calculate the band structure and charge transfer process between these oxide materials and hydrogen terminated diamond. Analysis of the band structures, density of states, Mulliken charges, adsorption energies and position of the Valence Band Minima (VBM) and Conduction Band Minima (CBM) energy levels shows that both oxides act as electron acceptors and inject holes into the diamond structure. Hence, those metal oxides can be described as p-type doping materials for the diamond. Additionally, our work suggests that by depositing appropriate metal oxides in an oxygen rich atmosphere or using metal oxides with high stochiometric ration between oxygen and metal atoms could lead to an increase of the charge transfer between the diamond and oxide, leading to enhanced surface transfer doping.

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