TD-B3LYP Method Research Articles

Benzene expansion Janus GC base analogues: A detailed theoretical study

Density Functional Theory (B3LYP) and Time Dependent Density Functional Theory (TD-B3LYP) computations have been used to investigate the electronic structural and optical properties of the newly designed benzene expansion Janus GC bases (J-GC1, J-GC2 and J-GC3), and the effect of water solution and base pairing also has been considered. The results show that the benzene expansion J-GC bases can pair with G and C simultaneously to form stable H-bonded WC base pairs. The lowest absorption and emission wavelengths of J-GC1¡¢J-GC2 and J-GC3 are red shifted compared with J-GC due to the increase of effective conjugation length with the introduction of benzene. The oscillator strengths of J-GC1¡¢J-GC2 and J-GC3 are similar. The water solution greatly influences the properties of the excited states and the first excitation and emission wavelength changes in the range of 16–65nm. The water solution can increase the oscillator strengths of the absorption and emission spectra. The TD-B3LYP method predicts that the lowest excitation of J-GC3:C and J-GC2:G are charge transfer states, while the other base pairs present local transitions on the J-GC base moieties. The first excitation wavelengths of these local transition base pairs change in the range of 6–18nm indicating that H-bonding interaction can influence the first excitation energy.

Optical absorption and emission properties of benzene-expanded Janus AT nucleobase analogues: A DFT study

We design benzene-expanded Janus AT bases (J-AT1, J-AT2, BF1 and BF2) and investigate the structural and optical properties of these bases using DFT and TDDFT methods and also consider the effect of water solution and base pairing. The results show that J-AT1 has a nonplanar structure and its amino group is more asymmetric than the other three bases. J-AT1 and BF1 exist intramolecular H-bonds. The Janus AT base pairs exist three intermolecular H-bonds: NH···N has the largest energy, followed by NH···O and CH···O. The Janus AT base pairs retain the strength of H-bonds and maintain the stability of the base pair. The lowest absorption and emission wavelengths of the benzene-expanded Janus AT bases are all assigned to ππ* character arising from HOMO to LUMO transition, and they exhibit redshift due to the increase in effective conjugation length with the introduction of benzene. The excited state assignments in water solution are one-to-one correspondence to those in gas phase. The lowest absorption and emission wavelength of J-AT1 is blueshift, while J-AT2, BF1 and BF2 bases are redshift as compared to those in gas. The TD-B3LYP method predicts that the first excitation wavelengths of Janus AT base pairs are local excitation on the Janus AT base moieties, which is coincident with the result of CAM-B3LYP and M062X functional. Base pair can influence the excitation properties of base monomer. The results obtained from this theoretical investigation confirm that the position of benzene ring significantly influences the structure and optical properties of the Janus AT bases.

Electronic structures and second hyperpolarizabilities of annulenes derivatives

Organic nonlinear optical materials have attracted considerable attention in recent years because of their potential applications in photonic devices and optical information processing. Recent studies have shown that annulene derivatives exhibit good second-order nonlinear optical properties, but their third-order nonlinear optical properties are studied little. In this paper, the values of molecular static linear polarizability α and second hyperpolarizability γ of substituted annulenes have been investigated with different levels of HF, B3LYP, BHandHLYP and CAM-B3LYP at different basis sets, respectively. Their ultraviolet spectra have also been calculated by using the TD-B3LYP method. It is found that the quality of the basis set is important for the hyperpolarizability calculations, and diffuse functions are important to obtain accurate results for the second hyperpolarizability. We also study the structure-optical property relationship for annulene. It is found that annulene molecular structure has a significant influence on third-order nonlinear optical response. Increasing the conjugation length and introducing push-pull electronic groups can enhance the second hyperpolarizability. But the introduction of push-pull electronic groups can enhance the hyperpolarizability more remarkably than increasing the conjugation length dose, which may be due to the fact that the introduction of push-pull electronic groups can provide a large number of polarizable electrons whereas increasing the conjugation length can only enhance the electron delocalization. Meanwhile the push-pull electronic group substituted annulenes can also exhibit high transparency in visible region. Thus, this work has a good reference for designing nonlinear optical material with high, nonlinear optical coefficient and good transparency. In addition, for the same push-pull electronic groups, the higher conjugation degree and the longer πup -conjugated bridge result in the decrease of HOMO-LUMO energy gap and transition energy which benefits the enhancement of nonlinear optical response. Our results demonstrate that annulene derivative shows both high transparency and large second hyperpolarizability, and thus becomes a promising candidate for third-order nonlinear optical material. In addition, the dynamic (hyper) polarizabilities of considered annulene molecules are calculated by using CAM-B3LYP method. It is found that in near-infrared region, with the increase of frequency of incident light, α (ω; ω), γ (-ω; ω, 0, 0) and γ (-2ω; ω, ω, 0) are all increased, and the near-resonance enhancement effect occurs. Under the condition of far resonance, α (ω; ω), γ (-ω; ω, 0, 0) and γ (-2ω; ω, ω, 0) change little. This dispersion effect may be helpful for the experimental study and applications as well.

Quantum chemical analysis of salen–aluminum complexes for organic light emitting diodes

Molecular structures, molecular orbital characteristics, and electronic properties of salen–aluminum complexes in organic light emitting diodes have been investigated by quantum chemical calculations to elucidate emission properties. The first excited-state structures were optimized by CIS and TD-CAM-B3LYP and their emission wavelengths were obtained from TD-CAM-B3LYP. Absorption and emission wavelengths from TD-CAM-B3LYP reproduced experimental values. The TD-B3LYP method is not adequate to calculate the transition energies for the first excited-state of salen–aluminum complexes. The structural changes and electronic transition during the excitation process and the tendency in absorption and emission wavelengths have been interpreted by frontier molecular orbitals.

Synthesis, spectroscopic properties and theoretical studies of bis-Schiff bases derived from polyamine and pyrazolones

A series of novel bis-Schiff base were synthesized from 1-aryl-3-methyl-4-benzoyl-5-pyrazolones and diethylenetriamine (or triethylenetetramine) as the starting materials. All of these bis-Schiff bases were characterized by means of NMR, IR, and MS. The UV–vis absorption spectra and fluorescent spectra of these bis-Schiff bases were also measured. Moreover, the B3LYP/6-31G(d) method was used to optimize the ground state geometry of the bis-Schiff bases; and the UV–vis spectroscopic properties of the products were computed and compared with corresponding experimental data based on cc-pVDZ basis set of TD-B3LYP method. It has been found that all of these bis-Schiff bases show a remarkable absorption peak in a wavelength range of 270–340nm; and their maximum emission peaks are around 348nm.

Crystal structure characterization as well as theoretical study of spectroscopic properties of novel Schiff bases containing pyrazole group

A series of novel Schiff bases containing pyrazole group were synthesized using 1-aryl-3-methyl-4-benzoyl-5-pyrazolone and phenylenediamine as the starting materials. All as-synthesized Schiff bases were characterized by means of NMR, FT-IR, and MS; and the molecular geometries of two Schiff bases as typical examples were determined by means of single crystal X-ray diffraction. In the meantime, the ultraviolet-visible light absorption spectra and fluorescent spectra of various as-synthesized products were also measured. Moreover, the B3LYP/6-1G(d,p) method was used for the optimization of the ground state geometry of the Schiff bases; and the spectroscopic properties of the products were computed and compared with corresponding experimental data based on cc-pVTZ basis set of TD-B3LYP method. It has been found that all as-synthesized Schiff bases show a remarkable absorption peak in a wavelength range of 270–370nm; and their maximum emission peaks are around 344nm and 332nm, respectively.

Synthesis of Benzimidazoles Containing Pyrazole Group and Quantum Chemistry Calculation of Their Spectroscopic Properties and Electronic Structure

Five benzimidazole compounds containing pyrazole group were synthesized via one-step reaction of o-phenylenediamine and 1-arylpyrazole-4-carbaldehyde in ethanol under mild conditions. The composition and structure of resultant benzimidazole compounds were analyzed by means of elemental analysis, mass spectrometry, (1)H-nuclear magnetic resonance spectroscopy and X-ray single crystal diffraction. The ultraviolet-visible light spectra and fluorescent spectra of the products were measured. Their ground-state (S(0)) equilibrium geometries and vibrational frequencies were determined based on B3LYP method, and their first excited-state (S(1)) geometries were fully optimized based on 6-31G (d, p) basis set of TD-B3LYP method. Besides, the spectroscopic properties of the products were computed based on cc-pVTZ basis set of TD-B3LYP method and compared with corresponding experimental data. It has been found that benzimidazole compounds containing pyrazole group can be readily synthesized in a high yield via one-step reaction of o-phenylenediamine and 1-arylpyrazole-4-carbaldehyde in ethanol solvent. The fluorescence properties of the five synthesized compounds are closely related to their molecular structure; and their computed fluorescence spectra well correspond to their experimental values. Moreover, they have stable structure and strong fluorescence, showing potential application in time-resolved fluoroimmunoassay and DNA probe.

Density functional theory predictions for blue luminescence and nonlinear optical properties of carbon-doped gallium nitride

The TD-B3LYP method and the plane-wave formalism of DFT method were applied to predict the blue luminescence and nonlinear optical effect of C-doped GaN, respectively. The introduction of carbon dopant will generate different acceptor or donor levels, which are mainly composed by p electronic state, within the energy gap of GaN. Exploring the calculated luminescence spectra based on the optimized excited-state structure, C N:GaN exhibits high luminescence intensity and has nice monochromatic property. In addition, the corresponding second-order nonlinear optical coefficients are considerable, χ (2) xzx =−15.07 pm/V and χ (2) zzz =26.91 pm/V, which are about 28 times and 50 times of the second-order optical coefficient of KDP crystal.

Theoretical insights into the trends in molecular properties of HCY, HSiY and HGeY molecules where Y = N, P, As

To obtain insights into the factors that govern the analogy between HCN and its isostructures, HXY where X = C, Si, Ge and Y = N, P, As, the electronic and structural properties of these species in ground, cationic and anionic states at the QCISD, MP2 and B3LYP levels with 6-311++G** basis set and the first exited state with TD-B3LYP method have been presented. The results suggest that there are some correlations between structural and thermodynamic properties of the smallest member of this group (HCN) and heavier congers. The results of computation at these levels also predict the stability of HCAs in the ground state and HCN, HSiN and HGeN in the cationic state from the energetic point of view. Molecular electrostatic potential map inspection shows that in HXN species nucleophilic region positions on N atom but in HXP and HXAs molecules by increasing the size of central atom nucleophilic region shifts from region near X atom toward terminal atom. Finally, the nature of bonds of HXY molecules are systematically studied through atoms in molecules (AIM) and natural bond orbital analyses (NBO).

A density functional theory study on photophysical properties of red light-emitting materials: Meso-substituted porphyrins

The density functional theory (DFT) has been applied to investigate the photophysical properties of meso-substituted porphyrins: 5,15-difluorenylporphyrin (DFP), 5,10,15,20-tetrafluorenylporphyrin (TFP), Zn-5,10,15,20-tetrafluorenylporphyrin (FPZ) and Zn-5,10,15,20-tetrafluorenoneporphyrin (OPZ). The geometry structures, frontier molecular orbitals, ionization potential (IP), electron affinity (EA) and reorganization energy ( λ) together with the absorption and emission wavelengths of these compounds were investigated. Theoretical calculations indicated that the introduction of meso-substitutions brought about significant effect on the photophysical properties. The TFP molecule has lowest hole injection energy barrier of all the studied compounds, and OPZ owns lowest electron injection energy barrier of them. The equilibrium of the hole and electron transport of FPZ is better than those of porphyrin (FBP), DPZ, TFP, and OPZ. The electron reorganization energies ( λ electron) of FBP, DFP, TFP, FPZ and OPZ are 0.22 eV, 0.20 eV, 0.23 eV, 0.26 eV and 0.13 eV, respectively, which are smaller than tris(8-hydroxyquinolinato) aluminum(III), thus these molecules are potential electron transport materials. Their visible absorption wavelengths are calculated by TD-B3LYP and semi-empirical ZINDO methods, and these results agree with corresponding experimental values. The fluorescence spectra of these complexes predicted by TD-HF method exhibit more consistent results with experimental data than by TD-B3LYP method.

Theoretical study of absorption and emission spectra of the monomer of PFBT

Conjugated polymers (CPs) have been used as highly responsive optical sensors for chemical and biological targets. The density functional theory (DFT), the time-dependent density functional theory (TDDFT) and the singly excited configuration interaction (CIS) approach were employed to simulate the absorption and emission spectra of a model monomer unit of the typical CP, poly[9,9′-bis-(6′- N, N, N-trimethylammonium)hexyl]fluorene-alt-4,7-(2,1,3-benzothiadiazole)] (PFBT). Various basis sets were applied in the calculations and their effects on the predictions for the optical properties of FBT are discussed. The results suggest that the TD-B3LYP method with basis sets larger than 6-311G(d,p) provides a suitable approach for investigations of the studied system.

Theoretical studies of the electronic structures and optical properties of stable blue-emitting polymer based on 4H-cyclopenta-[def]-phenanthrene

Geometries, ionization potentials (IPs), electron affinities (EAs) and optical properties of two series of π-conjugated oligomers (2,6-(4,4-bis(2-ethylthexyl)-4H-cyclopenta-[def]-phenanthrene))nCPPn (2,6-(4,4-bis(2-ethylthexyl)-8,9-dihydro-4H-cyclopenta-[def]-phenanthrene))nHCPPn (n=1–4) were studied theoretically. The ground and the excited state geometries were optimized by B3LYP and CIS methods with 6-31G∗ basis sets, respectively. The absorption and the emission spectra were calculated by TD-B3LYP method. The lowest-lying absorption is assigned to π→π∗ transition, and the fluorescence can be described as originating from the 1[ππ∗] excited state. IPs, EAs, H–L gaps, absorption and emission properties of PCPP (n=∞) and PHCPP (n=∞) were obtained by extrapolation method. The fact that the lowest-lying absorption and the emission of PCPP are blue-shifted compared with those of PHCPP, can be interpreted by the smaller effective repeating units of PCPP. The extra absorption band at 289nm of PCPP is contributed by the π→π∗ transition involving the extra π-conjugation CC bond.

Comparison of basis set effects and the performance of ab initio and DFT methods for probing equilibrium fluctuations

The electronic absorption and emission spectra of large molecules reflect the extent and timescale of electron-vibration coupling and therefore the extent and timescale of relaxation/reorganization in response to a perturbation. In this paper, we present a comparison of the calculated absorption and emission spectra of NADH in liver alcohol dehydrogenase (LADH), using quantum mechanical/molecular mechanical methods, in which we vary the QM component. Specifically, we have looked at the influence of basis set (STO-3G, 3-21G*, 6-31G*, CC-pVDZ, and 6-311G**), as well as the influence of applying the DFT TD-B3LYP and ab initio TD-HF and CIS methods to the calculation of absorption/emission spectra and the reorganization energy (Stokes shift). The ab initio TD-HF and CIS methods reproduce the experimentally determined Stokes shift and spectral profiles to a high level of agreement, while the TD-B3LYP method significantly underestimates the Stokes shift, by 45%. We comment on the origin of this problem and suggest that ab initio methods may be naturally more suited to predicting molecular behavior away from equilibrium geometries.

Properties of a New Fluorescent Cytosine Analogue, Pyrrolocytosine

Pyrrolocytosine is a novel, environment sensitive, fluorescent base that can be used in place of cytosine as a fluorescent marker in nucleic acids. In this work the results of a detailed computational investigation into the hybridization and photochemical properties of the base are reported. The interaction energy of the base pair formed between pyrrolocytosine and guanine, calculated at the MP2/6-31G(d,0.25)//HF/6-31G(d,p) level, was found to be -27.2 kcal mol(-1), comparing very favorably with the value calculated for the cytosine and guanine base pair, -25.8 kcal mol(-1). The wavelengths for the vertical transitions of pyrrolocytosine and cytosine were determined using both the configuration interaction technique, with singly excited configurations (CIS) and time-dependent density functional theory using the B3LYP functional (TDB3LYP). It was found that the spacing between the first pipi state and the first npi state was significantly larger in the case of pyrrolocytosine than cytosine, providing a rationale for the higher fluorescence quantum yield of the former. Hydrogen bonding of pyrrolocytosine to guanine did not affect the predicted fluorescence properties of pyrrolocytosine whereas stacking guanine above pyrrolocytosine, in a manner appropriate to B-form DNA, significantly reduced the predicted fluorescence. Calculations on the two base systems using the TDB3LYP method produced low-lying charge-transfer states which are not predicted when the CIS method is used and are not thought to be physically meaningful.

Modeling of configurations and third-order nonlinear optical properties of C(36) and C(34)X(2) (X=B,N).

Using the ab initio method, the geometrical structures of C(36) and the X (B,N)-doped isomers C(34)X(2) have been optimized. On the basis of the optimized structures, then, the third-order nonlinear optical polarizabilities gamma in the different optical processes of the third-harmonic generation, electric-field induced second-harmonic generation and degenerate four-wave mixing, and two-photon absorption (TPA) cross sections delta are calculated by using TDB3LYP method coupled with the sum-over-states method. The calculated results show that the one-photon allowed excitation process dominate the two-photon excitation process for C(36)-D(6h), whereas the two-photon allowed excitation process dominate the one-photon excitation process for C(36)-D(2d) and C(34)X(2) (B,N). It is found that the largest resonant TPA peaks of dopant fullerenes have a blueshift and the TPA cross sections have an enhancement compared with those of the parent fullerenes of isomers C(36)-D(6h) and C(36)-D(2d).