Time-dependent Functional Theory Research Articles

Theoretical study of the substituent effects on the ESIPT mechanism of salicylideneaniline and the TICT photochemistry reactions.

The study of salicylideneaniline (SA) and its derivatives is critical due to their special photophysical properties and environmental sensitivity. In this work, the density time-dependent functional theory (TDDFT) and complete-active-space self-consistent-field (CASSCF) methods were carried out to calculate the substituent effect on excited-state properties and dynamics of SA derivatives. We found the para-substitution triggers the excited-state intramolecular proton transfer (ESIPT) reaction, exhibiting the dual-fluorescent phenomena. However, the meta- and ortho-substitutions impel the non-radiative transition process along the minimum energy conical intersection (MECI), forming the twisted intramolecular charge transfer (TICT) state to prevent ESIPT. This investigation of substituent effects on the photochemical processes and photophysical properties will provide the benchmarks for the design of fluorescent materials.

DFT and TD-DFT Studies of D-π-A Organic Dye Molecules with Different Spacers for highly Efficient Reliable Dye Sensitized Solar Cells.

This study focuses on six D-π-A systems, utilizing diverse π-spacers as bridges. Comprehensive analysis through Density Functional Theory (DFT) and Time-dependent Functional Theory (TD-DFT) methods at B3LYP using 6-31G (d.p) basis set explores geometrical, electrical, optical, photovoltaic, and absorption properties. EHOMO, ELUMO, and energy gap (Egap), for all of these dyes have been determined and discussed using ground state optimization. TD-DFT calculates optical properties, unveiling enhanced excitation energies and HOMO-LUMO energy levels, indicative of improved electron injection and dye regeneration processes. Examination of energy gap, open-circuit voltage (VOC), free energy change (ΔGinject), light harvesting efficiency (LHE), and absorption spectra reveals D4 dye's lower Egap and robust absorption in the visible spectrum. Molecular tailoring emerges as a promising technique for optimizing D-π-A sensitizer design, offering potential advancements in DSSCs applications.

Photoinduced Dynamics of a Single-Walled Carbon Nanotube with a sp3 Defect: The Importance of Excitonic Effects.

Herein, we employed linear-response time-dependent functional theory nonadiabatic dynamic simulations to explore the photoinduced exciton dynamics of a chiral single-walled carbon nanotube CNT(6,5) covalently doped with a 4-nitrobenzyl group (CNT65-NO2). The results indicate that the introduction of a sp3 defect leads to the splitting of the degenerate VBM/VBM-1 and CBM/CBM+1 states. Both the VBM upshift and the CBM downshift are responsible for the experimentally observed redshifted E11* trapping state. The simulations reveal that the photoinduced exciton relaxation dynamics completes within 500 fs, which is consistent with the experimental work. On the other hand, we also conducted the nonadiabatic carrier (electron and hole) dynamic simulations, which completely ignore the excitonic effects. The comparison demonstrates that excitonic effects are indispensable. Deep analyses show that such effects induce several dark states, which play an important role in regulating the photoinduced dynamics of CNT65-NO2. The present work demonstrates the importance of including excitonic effects in simulating photoinduced processes of carbon nanotubes. In addition, it not only rationalizes previous experiments but also provides valuable insights that will help in the future rational design of novel covalently doped carbon nanotubes with superior photoluminescent properties.

Predictive study, using density functional theory and time dependent functional theory, on the structure-property quantification of methylene blue and methyl red dyes for the application in organic solar cells

In this work, two organic materials as dyes, namely, methylene blue (MB) and methyl red (MR), have been proposed to play the role of the electron donor in organic photovoltaic (OPV) cells. We use the PCBM as a well-known electron acceptor. The density functional theory (DFT) method has been used to determine the electrostatic potential and the frontier molecular orbitals (FMO), of the methylene blue (MB) and the methyl red (MR) compounds. Nonlinear optical (NLO) descriptors have been determined for the two compounds. The potential energy surface analysis has been performed by the DFT method using the exchange and correlation of Becke, Lee, Yang, and Parr Gradient Corrected Functional (B3LYP) with the standard 6-31G(d) base. We have performed another theoretical study using quantum time-dependent density functional theory (TD-DFT) on both MB and MR as organic dyes to determine their UV-Vis spectra. The results of the energy gap, chemical hardness, dipole moment, and hyperpolarizability show that MB may be chemically more reactive Than MR. The present work has proposed a bilayer organic photovoltaic (OPV) cell to contribute to the valorization of the two dyes as solar materials. The developed photovoltaic cell project has used electrical and energetic parameters that can describe the OPV cell based on ([MB or MR]: PCBM). Open-circuit voltage (Voc), excitation energy, and oscillator strength have been theoretically determined. The results of the present work showed a remarkably high open circuit voltage, especially in the case of methyl red (1.55 V) more than in the case of the methylene blue (0.84 V) so that both of the two dyes can be a good candidate for organic solar cells.

Effect of number of donor–acceptor repeat units and macrocyclic configuration on excited state properties in TADF emitters: A multiscale theoretical study

Thermally Activated Delayed Fluorescent (TADF) molecules with Donor (D) -Acceptor (A) –Donor-Acceptor π-Conjugated Macrocycle structures have broad application potential in organic light-emitting diodes. In this paper, three D − A line type and one D − A − D − A π‑Conjugated Macrocycle molecules with same donor and acceptor groups are investigated using polarizable continuum model (PCM) combined with density functional theory (DFT) and time-dependent functional theory (TD-DFT) in solvent and film. It is found that the macrocyclic structure has a smaller energy gap (ΔEST) between the first singlet excited state (S1) and the first triplet excited state (T1) than the linear structure. The TADF efficiency is also analyzed based on the calculation of spin–orbit coupling (SOC) and the (reverse) intersystem crossing (RISC) rates between S1 and T1. The macrocyclic molecules have larger SOC and faster RISC rates, which also well explains the experimental predictions and results.

Photovoltaic response promoted via intramolecular charge transfer in pyrazoline-based small molecular acceptors: Efficient organic solar cells

Herein, a series of pyrazoline based non-fullerene compounds (THP1-THP8) having ladder-like backbone was designed by structural modulation with various electron accepting moieties. The density functional theory (DFT) and time-dependent functional theory (TD-DFT) study was executed at M06/6-311G(d,p) level for structural optimization and to determine the electronic and optical characteristics of the pyrazoline based chromophores. The optimized structures were employed to execute frontier molecular orbital (FMO), transition density matrix (TDM), density of state (DOS), open circuit voltage (Voc) and reorganization energy analyses at the aforementioned level of DFT to comprehend the photovoltaic (PV) response of THP1-THP8. The red-shifted absorption spectrum (512.861–584.555 nm) with reduced band gap (2.507–2.881 eV) allow considerable charge transferal from HOMO to LUMO in all the studied compounds. Global reactivity parameters (GRPs) demonstrated high softness with considerable reactivity in THP1-THP8. Moreover, remarkable Voc values (2.083–2.973 V) were noted for all the derivatives (THP1-THP8). However, THP2 with lowest energy gap (2.364 eV), highest λmax (617.482 nm) and softness (0.423 eV) values is considered good candidate among afore-said chromophores. Hence, the studied chromophores with efficient properties are appropriate for experimentalists in terms of manufacturing of efficient OSCs.

BODIPY Dimers with a Fused and Coplanar Structure: Photophysical Comparison, Low Threshold for Amplified Spontaneous Emission, and Deep-Red Bio-Imaging/Photodynamic Therapy Application.

Boron dipyrromethene (BODIPY)-derived dyes are generally superior emitters, but their absorption and emission fail to match the bio-active optical window (650-900 nm). In this work, we explored four bisBODIPY dyes (PB1-PB4) with easy-to-go synthesis, good solubility, high photostability, and high emission quantum yield in the deep-red region. Methyl and ethyl groups were introduced in these BODIPY dyes to improve their solubility. PB4 having a fused coplanar plane was synthesized and compared to PB1-PB3 having a non-fused structure. Their geometric structure was confirmed by single-crystal analysis, and their electronic structure, along with one-photon and two-photon absorptions, was analyzed by time-dependent functional theory calculation. Their absorption/emission spectra, emission quantum yields, and lifetimes were compared. It was found that the fused coplanar structure successfully red shifted PB4 absorption/emission to the deep-red region (698/720 nm), with a quantum yield of 0.58. PB4 showed an amplified spontaneous emission effect with an output efficiency of 6.0% at a pumping power of 3000 μJ. An improved photodynamic therapy (PDT) performance was observed from PB4 via in vitro and in vivo experiments. The practical PDT performance was evaluated by cell availability. Upon a 980 nm laser radiation of 5 min, the cell viability was decreased to ∼15%.

Solar driven CO2 hydrogenation to HCOOH on (TiO2)n (n = 1-6) atomic clusters.

Artificial photosynthesis is a crucial reaction that addresses energy and environmental challenges by converting CO2 into fuels and value-added chemicals. However, efficient catalytic activity using earth-abundant materials can be challenging due to intrinsic limitations. Herein, we explore neutral (TiO2)n (n = 1-6) atomic clusters for CO2 hydrogenation via comprehensive ab initio calculations combined with time-dependent functional theory. Our results show that these (TiO2)n clusters exhibit outstanding thermodynamic stabilities and decent surficial activities for CO2 activation and H2 dissociation, both of which possess kinetic barriers down to 0-0.74 eV. We establish a relationship between the binding strength of *CO2 species and electron characterization for these (TiO2)n clusters. These clusters, which have a wide energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccpied molecular orbital (LUMO) that allows them to harvest the solar light in the ultraviolet regime, enabling efficient catalysis for driving the catalysis of CO2 conversion. They provide exclusive reaction channels and high selectivity for yielding HCOOH products via the carboxyl mechanism, involving the kinetic barrier of the limiting step of 0.74-1.25 eV. We also investigated the substrate effect on supported (TiO2)n clusters, with non-metallic substrates featuring inert surfaces serving as suitable options for anchoring (TiO2)n clusters while preserving their intrinsic activity and selectivity. These computational results have significant implications not only for meeting energy demands but also for mitigating carbon emissions by utilizing CO2 as an alternative feedstock rather than considering it solely as a greenhouse gas.

Theoretical study on thermally activated delayed fluorescent molecules based on space charge transfer

Thermally Activated Delayed Fluorescent (TADF) molecules with through-space charge transfer (TSCT) have broad application potential in organic light-emitting diodes. In this paper, five TPA-ace based molecules with different electron-withdrawing groups and TSCT property are investigated using polarizable continuum model (PCM) combined with density functional theory (DFT) and time-dependent functional theory (TD-DFT) in Methylcyclohexane, Toluene and Dichloromethane. It is found that stronger electron-withdrawing ability of acceptors could induce redshift of emission and smaller energy gap between the first singlet excited state (S1) and the first triplet excited state (ΔEST). The ratio of TSCT to through bond charge transfer (TBCT) for S1 of TPA-ace-TRZ is calculated quantitatively, which further confirmed the TSCT character of TPA-ace-TRZ. The TADF property is also analyzed based on the calculation of spin–orbit coupling and the (reverse) intersystem crossing rates between S1 and T1. Our calculation results would favor the understanding of TSCT-TADF.

Photovoltaic properties and enhancement in near-infrared light absorption capabilities of acceptor materials for organic solar cell applications: A quantum chemical perspective via DFT

More than 22% power conversion efficiency (PCE) of organic solar cells (OSCs) has been reported with efficient narrow bandgap acceptor materials as the active layers. And end-capped modifications of such acceptor materials are an efficient approach for designing highly stable and efficient materials for organic solar cell applications. In this study, four new molecules (TOS1 to TOS4) are designed for the active layer of organic solar cells. Density functional theory and time-dependent functional theory have been employed for the computation of various geometric, photovoltaic, optoelectronic properties of newly designed molecules. Different analyses like frontier molecular orbitals, transition density matrix, open-circuit voltage, absorption maxima, excitation and binding energies have been performed and examined with great care. Further, reorganization energy of hole and electron of novel designed molecules has been calculated and results suggested that designed systems are effective contributors for future development of organic solar cells. Overall, the outcomes of this study urge the experimentalists for the future development of highly stable and near-infrared absorbing organic solar cells.

Time-dependent density functional theory study of the optical properties of tetrahedral aluminum nanoparticles.

The plasmonic properties of tetrahedral aluminum nanoparticles have been investigated using time-dependent functional theory (TDDFT) calculations. The excitation energies are calculated for tetrahedral aluminum nanoparticles (Aln , n =10-120) with different charge states. The BP86/DZ model is used to perform geometric optimization calculations for these clusters. The SAOP/DZ and LB94/DZ levels of theory have been used for the excitation energy calculations of these tetrahedral aluminum clusters. The absorption peaks are red-shifted upon increasing the size of the aluminum nanoparticles.

Diketopyrrolopyrrole based highly conjugated small molecules for organic solar cells

A series of three donor molecules (DPP-B, DPP-N and DPP-P) based on diketopyrrolopyrrole (DPP) sharing the similar backbone of D-π-A-π-D have been investigated. In these molecules, substituents such as pyrene, naphthalene and benzene act as the electron donating end groups, DPP as the central core unit and thiophene has been used as a bridge between donor and acceptor fragments. Theoretical calculations have been carried out with the help of density functional theory (DFT) and time-dependent functional theory (TD-DFT). For the optimization of geometry of investigated molecules, DFT functional B3LYP/6-31g(d) has been used and TD-B3LYP/6-31g(d) has been used to obtain the best results of calculations inexcited state. DPP-P has been considered a suitable donor molecule among all investigated molecules as it manifests the suitable value of Eg of 2.24 eV and showed the stronger absorption λmaxof 611 nm. Hence, this study reveals that investigated donor molecules are suitable for high performance organic solar cell devices

Theoretical investigation on rotaxanes containing a pyridyl-acyl hydrazone moiety: chemical Z → E and photochemical E → Z isomerizations

A theoretical calculation toward efficient control of a molecular shuttle of directional chemical Z → E and photochemical E → Z isomerization is reported. The fully optimized geometric structures are evaluated using five different functionals and are compared with the corresponding X-ray crystal structures. Frequency analysis is conducted on the basis of the optimized geometries to find the most stable state. The graphical user interface of the free molecular program VMD combined with the Multiwfn program is used to visualize the noncovalent interactions of the molecular shuttle. The time-dependent functional theory is used to calculate the ultraviolet absorption spectra of different isomers, excitation energies, and absorption wavelengths and then visualized them by a multifunctional wavefunction analyzer. The donor–acceptor interactions between the macrocycle and thread that constitute the molecular shuttle are probed through natural bond orbital calculations, and the transition state of the rotaxanes is calculated at the B3LYP-D3/6-311G(d,p) level. These calculations support the experimental observations of a large population ratio for Z ⇆ E.

Substitutional effect of different bridging groups on optical and charge transfer properties of small bipolar molecules for OLEDs

AbstractIn this work, a series of eight different bipolar molecules were designed and calculated using density functional theory (DFT) and time‐dependent functional theory (TD‐DFT) for organic light emitting diodes (OLEDs) as efficient luminescent and charge transfer materials. The eight donor‐π‐donor type small molecules (D1‐D8) were composed of triphenylamine (TPA) donor (D) unit connected to 1,8‐naphthalimides (NI) acceptor (A) unit though different π‐conjugated or R‐groups (as π‐spacer). The effect of substitutions made in π‐spacer was investigated on optical, electronic, and stability properties. This calculation analysis showed that different substitutions in π‐spacer resulted smaller Eg (range from 1.63 to 2.00 eV), broader absorption with the lowest excitation energy covering both visible and near infrared regions of solar spectrum, especially D3, D4, D5, and D6 molecules. The analyses of local densities of states, frontier molecular orbitals, and natural population analysis of orbitals revealed that studied molecules exhibited π‐π* electronic transitions of absorption in singlet excited states, but D5 and D6 also show intramolecular charge transfer (ICT) characteristics. The study of chemical indices, molecular electrostatic potential (MEP) surfaces, and charge transfer properties turned out that D4, D5, and D6 are expected to show good potential for luminescent and hole transport materials in the favor of OLEDs.

Benchmarking nonequilibrium Green’s functions against configuration interaction for time-dependent Auger decay processes

We have recently proposed a Nonequilibrium Green's Function (NEGF) approach to include Auger decay processes in the ultrafast charge dynamics of photoionized molecules. Within the so called Generalized Kadanoff-Baym Ansatz the fundamental unknowns of the NEGF equations are the reduced one-particle density matrix of bound electrons and the occupations of the continuum states. Both unknowns are one-time functions like the density in Time-Dependent Functional Theory (TDDFT). In this work we assess the accuracy of the approach against Configuration Interaction (CI) calculations in one-dimensional model systems. Our results show that NEGF correctly captures qualitative and quantitative features of the relaxation dynamics provided that the energy of the Auger electron is much larger than the Coulomb repulsion between two holes in the valence shells. For the accuracy of the results dynamical electron-electron correlations or, equivalently, memory effects play a pivotal role. The combination of our NEGF approach with the Sham-Schl\"uter equation may provide useful insights for the development of TDDFT exchange-correlation potentials with a history dependence.

Physicochemical studies on proton transfer reaction between methyl[5-(propylthio)-1H-benzoimidazole-2-yl]carbamate (albendazole, ABZ) with 2,4,6- trinitrophenol (picric acid, PA) in chloroform

In this study, a new proton transfer complex between albendazole drug (ABZ), methyl [5-(propylthio)-1H-benzoimidazole-2-yl]carbamate and picric acid (PA) has been synthesized and characterized in chloroform and solid state by different physicochemical methods. In chloroform, the proton transfer complex exhibited an absorption maxima at 409 nm. In addition, the complex was formed in a 1:1 molecular composition. The formation constant, spectroscopic physical parameters and enthalpy of formation confirmed that, the formed complex has high stability. The solid-state complex was also found in a 1:1 stoichiometric ratio from elemental analysis and was isolated as yellow crystals. Changes in vibrational mode wavenumbers and chemical shifts in infrared and 1H NMR spectra were found in comparison with the reactants, confirming the complex formation. Furthermore, TG/DTA analysis provided information about changes in material properties as a function of temperature. Density functional theory (DFT) at B3LYP/6-31G (d,p) level of the theory was employed to support the experimental results. The optimized structures of reactants and the new complex, their geometrical parameters, reactivity parameters, molecular electrostatic potential maps (MEP) and natural atomic charges from natural bond orbital (NBO) analysis were calculated. It has been concluded from the investigated computational analysis that the presence of many hydrogen bonds in the formed complex beside charge transfer interaction are certainly responsible for its high stability. Time-dependent functional theory (TD-DFT) at the same was applied to explain the origin of the recorded electronic transition in chloroform. A good consistency was found between experimental and theoretical results.

Structural, spectroscopic properties and theoretical studies of (E)-1-(4-Bromophenyl)-3-(2,3,4-trimethoxyphenyl)prop-2-en-1-one as a potential anti-oxidant agent

ABSTRACTThe new chalcone compound namely (E)-1-(4-Bromophenyl)-3-(2,3,4-trimethoxyphenyl)prop-2-en-1-one (C18H17BrO4) is crystallized in the monoclinic crystal system of P21/c space group. The unit cell dimensions are: a = 8.0753 (10) Å, b = 21.873 (3) Å, c = 9.3362 (12) Å, α = 90°, β = 99.369 (2), γ = 90° and Z = 4. The single crystal was grown using slow evaporation solution growth technique. The newly synthesized compound was characterized by using IR, 1H- and 13C-NMR, UV-Vis and single crystal X-ray diffraction analyses. Quantum chemical method of Density Functional Theory (DFT) with B3LYP/6-311++G(d,p) has been employed to study the structural and spectral properties of the compound. The electronic absorption spectrum was calculated using the time dependent functional theory (TDDFT) method. The most stable conformer of the title chalcone is identified from the computational results. Hirshfeld surface analysis with fingerprint plots has been used as a graphical tool for visualization and understanding of intermolecular interactions. Intermolecular C‒H····O interaction observed stabilize the crystal structure, forming an infinite one dimensional column. The effect of this intermolecular interaction in the solid state can be seen in the difference between the experimental and the theoretically optimized geometrical parameters. The crystal is transparent in the entire visible region and absorptive in the UV region. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping electron potential (MEP). The other molecular properties like charge transfer are explain using Mulliken population analysis. The antioxidant test indicated that the 2,3,4-trimethoxy substitution on the bromide chalcone to be one of the favorable modification to enhance its metal chelating activity.

Phenazine Fused Benzo Coumarins with Negative Solvatochromism and Positive Solvatochromic Emission--Synthesis, Photo Physical Properties, DFT and TDDFT Studies.

5-Hydroxybenzo[a]phenazine-6-carbaldehyde was synthesized and condensed with substituted active methylene compounds to obtain four novel phenazine fused coumarin dyes. Solutions of imidazole containing dyes in various solvents exhibited yellow to orange fluorescence while benzothiazole containing dyes showed brilliant bluish green fluorescence. The dyes showed pronounced negative solvatochromism. However, the emission experienced progressive red shift with increasing polarity. The excited states of these dyes are proved to be more polar than the ground state. The dyes showed fairly good quantum yield in the range 0.1-0.7, and displayed high thermal stability, as determined using thermo gravimetric analysis. The density functional theory computations showed that intramolecular charge transfer occurs from the 3 position to the 7 position. The excited state computation using time dependent functional theory predicted the emission well.

Synthesis, one and two-photon optical properties of two asymmetrical and symmetrical carbazole derivatives containing quinoline ring

The carbazole derivatives are suitable for two-photon absorption optical storage and photoluminescence material. Two carbazole derivatives, asymmetrical and symmetrical type molecules containing quinoline rings as electron acceptors and an N-ethylcarbazole group as electron donor, 9-ethyl-3-(2-quinolin)viny-carbazole (4) and 9-ethyl-3,6-bis(2-(quinolin)vinyl)-carbazole (5), had been synthesized by the Vilsmeier reaction of formylation and Knoevenagel condensation. The one-photon properties including absorption, fluorescence emission spectra, fluorescence quantum yields and fluorescence decay behaviors were investigated in N,N-dimethylformamide. Meanwhile, these compounds were theoretically surveyed by the density functional theory (DFT) and the time-dependent functional theory (TD-DFT). The two-photon excited fluorescence and two-photon absorption cross-sections were measured for the compounds by 120fs pulse at 800nm Ti: sapphire laser operating at 1kHz repetition rate. The results showed that both of the two compounds 4 and 5 had higher fluorescence quantum yield (Φ) of 0.77 and 0.81 comparing with carbazole. Compounds 5 with symmetric π conjugated structure possessed longer fluorescence lifetime (τ) of 21.4ns and larger two-photon absorption cross-sections (δTPA) of 364×10−50cm4s/photon than those of compounds 4 with asymmetric π conjugated structure (τ=10.03ns and δTPA=81×10−50cm4s/photon). It was indicated that the one and two-photon optical properties of carbazole derivatives are influenced strongly by the symmetry and length of π conjugated structure.

Excitation energies from range-separated time-dependent density and density matrix functional theory

Time-dependent density functional theory (TD-DFT) in the adiabatic formulation exhibits known failures when applied to predicting excitation energies. One of them is the lack of the doubly excited configurations. On the other hand, the time-dependent theory based on a one-electron reduced density matrix functional (time-dependent density matrix functional theory, TD-DMFT) has proven accurate in determining single and double excitations of H(2) molecule if the exact functional is employed in the adiabatic approximation. We propose a new approach for computing excited state energies that relies on functionals of electron density and one-electron reduced density matrix, where the latter is applied in the long-range region of electron-electron interactions. A similar approach has been recently successfully employed in predicting ground state potential energy curves of diatomic molecules even in the dissociation limit, where static correlation effects are dominating. In the paper, a time-dependent functional theory based on the range-separation of electronic interaction operator is rigorously formulated. To turn the approach into a practical scheme the adiabatic approximation is proposed for the short- and long-range components of the coupling matrix present in the linear response equations. In the end, the problem of finding excitation energies is turned into an eigenproblem for a symmetric matrix. Assignment of obtained excitations is discussed and it is shown how to identify double excitations from the analysis of approximate transition density matrix elements. The proposed method used with the short-range local density approximation (srLDA) and the long-range Buijse-Baerends density matrix functional (lrBB) is applied to H(2) molecule (at equilibrium geometry and in the dissociation limit) and to Be atom. The method accounts for double excitations in the investigated systems but, unfortunately, the accuracy of some of them is poor. The quality of the other excitations is in general much better than that offered by TD-DFT-LDA or TD-DMFT-BB approximations if the range-separation parameter is properly chosen. The latter remains an open problem.