Daengngern, Rathawat

Preferred name

Alternative Name

Daengngern, R.

Main Affiliation

School of Science

rathawat.da@kmitl.ac.th

Now showing 1 - 10 of 16

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Oxotitanium-porphyrin for selective catalytic reduction of NO by NH3: A theoretical mechanism study
(2018-01-01)
Daengngern, Rathawat
;
Maitarad, Phornphimon
;
Shi, Liyi
;
Zhang, Dengsong
;
Kungwan, Nawee
The reaction mechanism of the selective catalytic reduction of NO by NH<inf>3</inf> (NH<inf>3</inf>-SCR) on an oxotitanium-porphyrin catalyst was systematically investigated by using density functional theory calculations with the M06L functional. The reaction was proposed to follow the nitrite mechanism over the two forms of active sites; the oxotitanium-porphyrin Lewis acid site (TiO-por) and the Brønsted acid site (TiOH-por). The reaction path consisted of (i) nitrite formation, (ii) NH<inf>3</inf> oxidation, (iii) formation of NH<inf>2</inf>NO and NHNOH intermediates, and (iv) N<inf>2</inf> and H<inf>2</inf>O product formation. The obtained calculations showed that the formation of the NHNOH intermediate was the rate determining step for both active sites with the energy barriers (E<inf>a</inf>) of 32.2 and 36.2 kcal mol-1 for the Lewis and Brønsted acid sites, respectively. It is worth noting that the activation energy for NHNOH formation over the oxotitanium-porphyrin active sites was found to be in the same range as that of vanadium oxide cluster models. Furthermore, the product formations of N<inf>2</inf> and H<inf>2</inf>O over the Lewis and Brønsted acid sites of oxotitanium-porphyrin were exothermic processes with reaction energies (E<inf>r</inf>) of -67.1 and -39.0 kcal mol-1, respectively. Thus, in conclusion, the oxotitanium-porphyrin could theoretically act as an alternative catalyst for NH<inf>3</inf>-SCR of NO and it would be challenging to test it in experimental studies.
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A spectroscopic study of indigo dye in aqueous solution: A combined experimental and TD-DFT study
(2018-12-01)
Jiwalak, Naparat
;
Daengngern, Rathawat
;
Rungrotmongkol, Thanyada
;
Jungsuttiwong, Siriporn
;
Namuangruk, Supawadee
This study reports UV–Visible spectra and electronic structures of indigo (IG) in aqueous solution using a combination of experimental and theoretical methods. In the visible region, the experimental absorption spectrum of the solution showed a broad peak with the longest wavelength of maximal absorption (λ<inf>max</inf>) value at 708 nm. For the theoretical method, a trans-IG monomer and a trans-IG bound with two water molecules (IG.2W) were optimized in the ground state using the B3LYP and B3LYP-D3 calculations with the 6-31 + G(d,p) basis set and the SCRF-CPCM model for taking solvent effect into account was also applied. Sequentially, the UV–Visible spectra and λ<inf>max</inf> of the optimized trans-IG and IG.2W models in the implicit water were simulated by the time-dependent density functional theory (TD-DFT) calculations. The TD-DFT methods including BLYP, B3LYP, PBE0, CAM-B3LYP, M06-2X, ωB97XD, LC-BLYP, and LC-ωPBE functionals without and with the D3 correction and the 6-31 + G(d,p) basis set were selected. The results pointed out that BLYP and BLYP-D3 were the best methods because they could reproduce the experimental λ<inf>max</inf> value of IG in aqueous solution. The predicted λ<inf>max</inf> values of IG.2W were almost equal to 708 nm (the experimental data), indicating that IG.2W could be responsible for optical properties of IG.
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Theoretical Insights on Solvent Control of Intramolecular and Intermolecular Proton Transfer of 2-(2′-Hydroxyphenyl)benzimidazole
(2017-08-10)
Prommin, Chanatkran
;
Kanlayakan, Narissa
;
Chansen, Warinthon
;
Salaeh, Rusrina
;
Kerdpol, Khanittha
Excited-state proton transfer (ESPT) processes of 2-(2′-hydroxyphenyl)benzimidazole (HBI) and its complexation with protic solvents (H<inf>2</inf>O, CH<inf>3</inf>OH, and NH<inf>3</inf>) have been investigated by both static calculations and dynamics simulations using density functional theory (DFT) at B3LYP/TZVP theoretical level for ground state (S<inf>0</inf>) and time-dependent (TD)-DFT at TD-B3LYP/TZVP for excited state (S<inf>1</inf>). For static calculations, absorption and emission spectra, infrared (IR) vibrational spectra of O-H mode, frontier molecular orbitals (MOs), and potential energy curves (PECs) of proton transfer coordinate were analyzed. Simulated absorption and emission spectra show an agreement with available experimental data. The hydrogen bond strengthening in the S<inf>1</inf> state has been proved by the changes of IR vibrational spectra and bond parameters of the hydrogen moiety with those of the S<inf>0</inf> state. The MOs provide the visual electron density redistribution confirming the hydrogen bond strengthening mechanism. The PECs show that the proton transfer (PT) process is easier to occur in the S<inf>1</inf> state than the S<inf>0</inf> state. Moreover, on-the-fly dynamics simulations of all systems were carried out to provide the detailed information on time revolution. The results revealed that the excited-state intermolecular proton transfer for HBI is fast, whereas the excited-state intermolecular proton transfer for HBI with protic solvents are slower than that of HBI because the competition between intra- and intermolecular hydrogen-bonds between HBI and protic solvent. These intermolecular hydrogen-bonds hinder the formation of tautomer, hence explaining the low quantum yield found in the protic solvent experiment. Especially for HBI complexing with methanol, only ESIntraPT occurs with small probability compared to HBI with water and ammonia.
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Theoretical study on influence of geometry controlling over the excited-state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline and its derivatives
(2017-08-01)
Chansen, Warinthon
;
Salaeh, Rusrina
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Prommin, Chanatkran
;
Kerdpol, Khanittha
;
Daengngern, Rathawat
A structural modification on quinoline as a proton donor of 10-hydroxybenzo[h]quinoline (HBQ) giving different HBQ derivatives greatly affects their photophysical properties. In this study, the excited-state intramolecular proton transfer (ESIPT) reactions of HBQ and its derivatives with different geometries have been systematically investigated using DFT and TD-DFT at B3LYP/TZVP. Calculated absorption and emission spectra are used to describe the photophysical changes in which the absorption spectra of HBQ derivatives are blue-shifted compared with that of HBQ while their emission spectra are blue-shifted except those of 3,4-dihydro indene[1,2-b]pyrrole-8-ol (IPRO) and 2-(4H-pyrrol-2-yl)phenol (PRP) compounds with different proton donor and connecting moiety are red-shifted. From results of potential energy curves along the proton transfer (PT) coordinate, PT is favorable in the excited-state but not in the ground state. On-the-fly dynamics simulations in the excited-state are further employed to determine reaction mechanisms and the time evolution of PT. The ESIPT process easily occurs in most of the compounds except the IPRO with much high PT barrier. The ESIPT times in most compounds take place within 100 fs and PT probability is nicely anti-correlated with the PT barrier. Thus, the geometry changes alter the electronic spectra but do not affect ESIPT of HBQ derivatives. Moreover, once the PT is complete, the internal conversion is initiated by twisted skeleton, leading to lower intensity of tautomer emission.
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Tautomeric enhancement of 2-(1H-pyrazol-5-yl)pyridine in photoinduced proton transfer by water-assisted molecules
(2024-09-20)
Salaeh, Rusrina
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Inporn, Wutthana
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Chansen, Warinthon
;
Kungwan, Nawee
;
Daengngern, Rathawat
Theoretical insight of excited state proton transfer (ESPT) in 2-(1H-pyrazol-5-yl)pyridine abbreviated as PPP interacting with water wires: PPP(H<inf>2</inf>O)<inf>n</inf> where n = 1–3 has been presented in both static and dynamics studies. Explicit water molecules placed around PPP have been simulated to elucidate the intermolecular hydrogen bonding interactions between them. Hydrogen bond strengthening in the excited state (S<inf>1</inf>) has been verified by shorter bond distances and redshift of IR vibrational spectra involving the proton transfer (PT) process. Furthermore, on-the-fly excited state dynamics simulations of all complexes have been performed to provide detailed information on the PT mechanism. The dynamic results show that one water molecule added to the neighboring PPP as an intermolecular hydrogen bonding bridge can promote double excited state intermolecular proton transfer up to 36% compared with its intrinsic intramolecular hydrogen bond of the PPP system. Meanwhile adding a second or third water molecule could decrease the probabilities of PT. Especially in PPP(H<inf>2</inf>O)<inf>3</inf>, a rearrangement of water molecules is observed that PT occurs via one water molecule. Hence, the models with explicit water molecules interacting with PPP as intermolecular hydrogen bonding bridge are a great representative role played by water molecules of the PT process at the molecular level.
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The effect of protic solvents on the excited state proton transfer of 3-hydroxyflavone: A TD-DFT static and molecular dynamics study
(2018-02-01)
Salaeh, Rusrina
;
Prommin, Chanatkran
;
Chansen, Warinthon
;
Kerdpol, Khanittha
;
Daengngern, Rathawat
The effect of intermolecular hydrogen bonding played by protic solvents (ammonia, methanol and water) on the excited state proton transfer (ESPT) reaction of 3-hydroxyflavone (3HF) was theoretically investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT). The formation of intermolecular hydrogen bond induced by protic solvents indicates that the intramolecular hydrogen bond may be interrupted in favor of a complex causing low quantum yield of keto emission and exhibiting dual emission (both enol and keto) in experiment. The strengthening of intermolecular hydrogen bond in the S<inf>1</inf> state has been confirmed by the red-shift of IR vibrational spectra and shorter bond distances involving proton transfer (PT) process in comparison with those of the S<inf>0</inf> state. From potential energy curves (PECs) of PT coordinate, PT process is likely to proceed in S<inf>1</inf> state and PT in 3HF(NH<inf>3</inf>) occurs more easily than those of 3HF(CH<inf>3</inf>OH) and 3HF(H<inf>2</inf>O) due to its lower barrier. Moreover, on-the-fly dynamics simulations of all complexes were carried out to provide the detailed information on the PT mechanism. The dynamic results show that ESPT process of 3HF with protic solvent takes place through intermolecular hydrogen bond with slower PT time (259, 117 and 104 fs for 3HF(NH<inf>3</inf>), 3HF(CH<inf>3</inf>OH) and 3HF(H<inf>2</inf>O), respectively) than that of 3HF (76 fs) via intramolecular hydrogen bond. Furthermore, the ultrafast PT time is found to be nicely correlated with polarity of solvent and PT probability is also anti-correlated with PT barrier.
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Excited-state intramolecular proton transfer reactions of 2,5-bis(2′-benzoxazolyl)hydroquinone and its water cluster exhibiting single and double proton transfer: A TD-DFT dynamics simulation
(2019-07-15)
Daengngern, Rathawat
;
Salaeh, Rusrina
;
Saelee, Tinnakorn
;
Kerdpol, Khanittha
;
Kungwan, Nawee
Detailed pictures of the excited-state intramolecular proton transfer (ESIPT)of 2,5-bis(2′-benzoxazolyl)hydroquinone (BHQ)and its water cluster have been investigated by dynamics simulations on the first lowest-excited energy using time-dependent density functional theory (TD-DFT). We focused on the structural, photophysical and dynamic properties of BHQ in the absence and presence of water molecules through intermolecular hydrogen bonds (interHBs). Our dynamics simulations reveal three possible mechanisms of the ESIPT processes: i)no proton transfer (No PT); ii)single PT (SPT); and iii)double PT (DPT), that could take place within the PT time of 160 fs via intrinsic intramolecular hydrogen bonds (intraHBs). The ESIPT mechanism of isolated BHQ elucidates that back PT is likely to be found at 64% rather than the SPT (32%)and DPT (4%), which is in good agreement with the experiments of dual fluorescence from di-enol and mono-keto emissions. Notably, the results from BHQ with water (BHQ-(H<inf>2</inf>O)<inf>2</inf>)reveal that the participation of water might produce a remarkable effect on promoting the SPT process up to 60% and DPT up to 7 times when compared to conditions of no water. The simulated probability of PT is well related to possible PT mechanisms regarding different tautomers in the fluorescence spectra found in previous experiments. The existence of di-keto tautomer arose from the DPT of BHQ and its water cluster and was not observed in the UV/Vis spectrum.
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A theoretical investigation into the demethylation mechanism of dimethylsulfide over the W3O6 cluster
(2025-07-01)
Aziz, Hafiz Aji
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Kungwan, Nawee
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Gleeson, Duangkamol
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Saelee, Tinnakorn
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Daengngern, Rathawat
Understanding how dimethyl sulfide (DMS) breaks down to form value-added products such as methanol on transition metal oxide catalysts is important for improving desulfurization processes. In this study, the reaction mechanism over a tungsten oxide cluster (W₃O₆) is elucidated using density functional theory (DFT) at the M06-L/LANL2DZ/aug-cc-pVTZ level of theory. Two competing mechanistic pathways were discovered over the W₃O₆ cluster: Pathway A) direct demethylation followed by methanol desorption and Pathway B) a water-assisted concerted demethylation pathway. Pathway A involves sequential steps with a moderate demethylation barrier (49.43 kcal/mol), but a significantly higher barrier (68.78 kcal/mol) for subsequent methanol formation, imposing a kinetic bottleneck. Remarkably, Pathway B, mediated by an explicit water molecule, facilitates a lower-barrier concerted transformation (56.19 kcal/mol), effectively bypassing the high-energy intermediate. Kinetic modeling via Transition State Theory and the Energetic Span Model reveal that despite the very low turnover frequency (TOF = 9.29 × 10−30 s⁻¹), the water-assisted pathway is energetically superior. These findings highlight the important role of water in helping the reaction proceed and offer insight for designing better catalysts for sulfur removal from DMS to methanol over the W₃O₆ cluster.
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Experimental and Theoretical Exploration of Ultrafast Excited State Double Proton Transfer in 2,5-Bis(2-benzimidazolyl)hydroquinone
(2025-07-01)
Prommin, Chanatkran
;
Chaihan, Komsun
;
Daengngern, Rathawat
;
Mori, Seiji
;
Akutsu-Suyama, Kazuhiro
The electronic properties and excited-state intramolecular double proton transfer of 2,5-bis(2-benzimidazolyl)hydroquinone (bis-HBI) in a nonpolar solvent were investigated using a combined experimental and theoretical approach. Bis-HBI was successfully synthesized and its characterization was confirmed through 1H NMR and FT-IR. Three distinct emission peaks of bis-HBI were observed at 484, 597, and 730 nm, which were theoretically assigned to the di-enol (EE), mono-keto (EK), and di-keto (KK) species, respectively. The emission peaks at longer wavelengths (597 and 730 nm) are attributed to tautomerization upon photoexcitation and are assigned to the mono-keto and di-keto species, which result from multiple proton transfers. These species exhibit kinetically and thermodynamically favorable behaviors. On-the-fly dynamics simulations reveal that the double proton transfer process occurs ultrafast, within 433 fs. Additionally, both backward and forward proton transfers are observed during the first and second proton transfers, indicating tautomeric equilibria between the three species—EE, EK, and KK—on the excited-state surface. This is consistent with the potential energy surface along the proton transfer coordinate.
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Effect of water microsolvation on the excited-state proton transfer of 3-hydroxyflavone enclosed in -cyclodextrin
(2021-02-02)
Kerdpol, Khanittha
;
Daengngern, Rathawat
;
Sattayanon, Chanchai
;
Namuangruk, Supawadee
;
Rungrotmongkol, Thanyada
The effect of microsolvation on excited-state proton transfer (ESPT) reaction of 3-hydroxyflavone (3HF) and its inclusion complex with -cyclodextrin (-CD) was studied using computational approaches. From molecular dynamics simulations, two possible inclusion complexes formed by the chromone ring (C-ring, Form I) and the phenyl ring (P-ring, Form II) of 3HF insertion to -CD were observed. Form II is likely more stable because of lower fluctuation of 3HF inside the hydrophobic cavity and lower water accessibility to the encapsulated 3HF. Next, the conformation analysis of these models in the ground (S0) and the first excited (S1) states was carried out by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, respectively, to reveal the photophysical properties of 3HF influenced by the -CD. The results show that the intermolecular hydrogen bonding (interHB) between 3HF and -CD, and intramolecular hydrogen bonding (intraHB) within 3HF are strengthened in the S1 state confirmed by the shorter interHB and intraHB distances and the red-shift of O-H vibrational modes involving in the ESPT process. The simulated absorption and emission spectra are in good agreement with the experimental data. Significantly, in the S1 state, the keto form of 3HF is stabilized by -CD, explaining the increased quantum yield of keto emission of 3HF when complexing with -CD in the experiment. In the other word, ESPT of 3HF is more favorable in the -CD hydrophobic cavity than in aqueous solution.

Daengngern, Rathawat

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