Electronically excited state structures and stabilities of organic small molecules: A DFT study of triphenylamine derivatives

Gong, Kun; Yang, Jieqiong; Testoff, Thomas T.; Li, Wei; Wang, Tianyang; Liu, Dongzhi; Zhou, Xueqin; Wang, Lichang

doi:10.1016/j.chemphys.2021.111256

Cited by 8 publications

(7 citation statements)

References 71 publications

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“…The same computational practices were employed in our previous DFT studies of organic small molecules. [108][109][110]…”

Section: Computational Detailsmentioning

confidence: 99%

DFT and TDDFT Studies of Silicon Analogs of Fluorescein Derivatives

Weerasinghe

Wang

2023

Preprint

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Fluorescein derivatives play an important role in the field of biological and fluorescent sensors. To tune the spectroscopic properties many attempts have been made including extending conjugation, substituting the central carbon by nitrogen or introducing electron withdrawing groups and replace the oxygen bridge atom by other elements such as N, C, S, Se, and Te. In this paper we report density functional theory (DFT) and time-dependent DFT (TDDFT) studies of silicon analog of fluorescein derivatives with oxygen replaced by Si, C, and Ge. Among the different silicon analogs, the most conjugated molecule 4 showed red shift in absorption wavelength (495 nm). The OH position of molecule 2 has a significant effect on the spectral properties of the silicon analogs of the fluorescein. Since aggregation is very common in most of the fluorescein and it is interesting to study the effect of aggregation, we also studied dimerization of molecule 1 in silicon analog of fluorescein derivative and the results show that two absorption bands are formed with red shift compared to monomer.

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“…The same computational practices were employed in our previous DFT studies of organic small molecules. [108][109][110]…”

Section: Computational Detailsmentioning

confidence: 99%

DFT and TDDFT Studies of Silicon Analogs of Fluorescein Derivatives

Weerasinghe

Wang

2023

Preprint

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“…All calculations were performed using Gaussian09 80 software and the same computational procedures and convergences were used in the previous studies. [81][82][83][84][85][86] Both the proton affinity and gas phase acidity 87 were also calculated for the possible isomers of the protonated, neutral, and deprotonated species of halogen-substituted 2,4-dihydroxybenzoic acid. Optimizations were carried out using the B3LYP functional 88 with a basis set 6-31g+(d,p).…”

Section: Computational Detailsmentioning

confidence: 99%

DFT studies of proton transfer of 2, 4-dihydroxybenzoic acid derivatives

Bridgmohan

Wang

2023

Preprint

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In this work, the proton transfer and photophysical properties of 2,4-dihydroxybenzoic acid and its chlorinated and brominated derivatives were studied using Density Functional Theory (DFT) to understand the proton transfer mechanism of these molecules as matrices in matrix-assisted laser desorption-ionization (MALDI). Structures, IR, UV-Vis, and fluorescence spectra were obtained together with the energies of frontier orbitals from DFT and time-dependent DFT calculations. In addition, the proton affinity (PA) and gas phase acidity (GPA) of the molecules were determined to understand the heavy atom substitution effect. Upon substitution of Cl and Br, the UV-Vis absorption at ~330 nm increases with heavy atom substitutions. While no apparent change in the OH bond strength at the ground state, it is substantially weakened upon electronic excitation at both the first singlet and triplet excited states under heavy atom substitution. These results demonstrate that both the UV-Vis absorption and intersystem crossing play important roles in facilitating proton transfer in heavy atom substitution of 2,4-dihydroxybenzoic acid.

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“…The B3LYP functional has been widely used in vibrational studies of molecules, 77−83 and it is also used in the studies of electronic transitions in molecules 84−91 or reactions of molecules 92−96 where further tests on feasible functionals are still needed. 86,88,97 In future investigations, machine learning algorithms may also be utilized in the studies. 98−100 Seven basis sets, 6-31G(d,p), 6-31+G(d,p), 6-31++G(d,p), 6-311G-(d,p), 6-311+G(d,p), 6-311++G(d,p), and 6-311++G(df,pd), were employed to investigate the sensitivity of DFT results on the basis set.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Each DFT calculation was performed by using B3LYP. The B3LYP functional has been widely used in vibrational studies of molecules, − and it is also used in the studies of electronic transitions in molecules − or reactions of molecules − where further tests on feasible functionals are still needed. ,, In future investigations, machine learning algorithms may also be utilized in the studies. − Seven basis sets, 6-31G(d,p), 6-31+G(d,p), 6-31++G(d,p), 6-311G(d,p), 6-311+G(d,p), 6-311++G(d,p), and 6-311++G(df,pd), were employed to investigate the sensitivity of DFT results on the basis set. The basis set dependence was studied previously for UV–vis spectra of various organic small molecules. , In this work, these basis sets were chosen to understand the perturbation of electronic properties to the sensitive vibrational couplings to gain insight into the IR spectra.…”

Section: Computational Detailsmentioning

confidence: 99%

Effects of the Intramolecular Group and Solvent on Vibrational Coupling Modes and Strengths of Fermi Resonances in Aryl Azides: A DFT Study of 4-Azidotoluene and 4-Azido-N-phenylmaleimide

Perera,

Aikawa,

Shaner

et al. 2023

J. Phys. Chem. A

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The high transition dipole strength of the azide asymmetric stretch makes aryl azides good candidates as vibrational probes (VPs). However, aryl azides have complex absorption profiles due to Fermi resonances (FRs). Understanding the origin and the vibrational modes involved in FRs of aryl azides is critically important toward developing them as VPs for studies of protein structures and structural changes in response to their surroundings. As such, we studied vibrational couplings in 4-azidotoluene and 4-azido-N-phenylmaleimide in two solvents, N,N-dimethylacetamide and tetrahydrofuran, to explore the origin and the effects of intramolecular group and solvent on the FRs of aryl azides using density functional theory (DFT) calculations with the B3LYP functional and seven basis sets, 6-31G(d,p), 6-31+G(d,p), 6-31++G(d,p), 6-311G(d,p), 6-311+G(d,p), 6-311++G(d,p), and 6-311++G(df,pd). Two combination bands consisting of the azide symmetric stretch and another mode form strong FRs with the azide asymmetric stretch for both molecules. The FR profile was altered by replacing the methyl group with maleimide. Solvents change the relative peak position and intensity more significantly for 4-azido-N-phenylmaleimide, which makes it a more sensitive VP. Furthermore, the DFT results indicate that a comparison among the results from different basis sets can be used as a means to predict more reliable vibrational spectra.

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Electronically excited state structures and stabilities of organic small molecules: A DFT study of triphenylamine derivatives

Cited by 8 publications

References 71 publications

DFT and TDDFT Studies of Silicon Analogs of Fluorescein Derivatives

DFT and TDDFT Studies of Silicon Analogs of Fluorescein Derivatives

DFT studies of proton transfer of 2, 4-dihydroxybenzoic acid derivatives

Effects of the Intramolecular Group and Solvent on Vibrational Coupling Modes and Strengths of Fermi Resonances in Aryl Azides: A DFT Study of 4-Azidotoluene and 4-Azido-N-phenylmaleimide

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