Infrared Spectroscopy and Quantum Chemical Calculations of OH-(H2O)n Complexes

Tsuji, Kentaro; Shibuya, Kazuhiko

doi:10.1021/jp903648z

Cited by 50 publications

(71 citation statements)

References 28 publications

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“…Table reports the harmonic vibrational frequencies and zero‐point vibrational energies (ZPVEs) for all the stationary points of the Br + (H 2 O) 2 reaction predicted with the CCSD(T) method. Our vibrational frequencies for HBr, (H 2 O) 2 , and (H 2 O)OH are in general agreement with the available experimental results . The transition state has an imaginary vibrational frequency of 843 i cm −1 (cc‐pVDZ‐PP), 564 i cm −1 (cc‐pVTZ‐PP), or 518 i cm −1 (cc‐pVQZ‐PP), with the corresponding normal mode revealing simultaneous BrH4 bond formation and O2H4 bond breaking as the reaction proceeds toward products HBr + (H 2 O)OH.…”

Section: Resultssupporting

confidence: 88%

“…Our vibrational frequencies for HBr, (H 2 O) 2 , and (H 2 O)OH are in general agreement with the available experimental results. [33][34][35][36][37][38][39][40][41] The transition state has an imaginary vibrational frequency of 843i cm 21 (cc-pVDZ-PP), 564i cm 21 (cc-pVTZ-PP), or 518i cm 21 (cc-pVQZ-PP), with the corresponding normal mode revealing simultaneous BrAH4 bond formation and O2AH4 bond breaking as the reaction proceeds toward products HBr 1 (H 2 O)OH. Table 1 shows that the Br(H 2 O) 2 ZPVE corrections with different basis sets are surprisingly similar.…”

Section: Comparisons With F 1 (H 2 O) 2 and CL 1 (H 2 O)mentioning

confidence: 99%

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The Reaction between Bromine and the Water Dimer and the Highly Exothermic Reverse Reaction

Wang

et al. 2015

J Comput Chem

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The entrance complex, transition state, and exit complex for the bromine atom plus water dimer reaction Br + (H2O)2 → HBr + (H2O)OH and its reverse reaction have been investigated using the CCSD(T) method with correlation consistent basis sets up to cc-pVQZ-PP. Based on the CCSD(T)/cc-pVQZ-PP results, the reaction is endothermic by 31.7 kcal/mol. The entrance complex Br⋯(H2O)2 is found to lie 6.5 kcal/mol below the separated reactants. The classical barrier lies 28.3 kcal/mol above the reactants. The exit complex HBr⋯(H2O)OH is bound by 6.0 kcal/mol relative to the separated products. Compared with the corresponding water monomer reaction Br + H2 O → HBr + OH, the second water molecule lowers the relative energies of the entrance complex, transition state, and exit complex by 3.0, 3.8, and 3.7 kcal/mol, respectively. Both zero-point vibrational energies and spin-orbit coupling effects make significant changes to the above classical energetics. Including both effects, the predicted energies relation to separated Br + (H2O)2 are -3.0 kcal/mol [Br···(H2O)2 ], 28.2 kcal/mol [transition state], 26.4 kcal/mol [HBr···(H2O)OH], and 30.5 kcal/mol [separated HBr + (H2O)OH]. The potential energy surface for the Br + (H2O)2 reaction is related to that for the valence isoelectronic Cl + (H2O)2 system but radically different from the F + (H2O)2 system.

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Section: Resultssupporting

confidence: 88%

Section: Comparisons With F 1 (H 2 O) 2 and CL 1 (H 2 O)mentioning

confidence: 99%

The Reaction between Bromine and the Water Dimer and the Highly Exothermic Reverse Reaction

Wang

et al. 2015

J Comput Chem

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“…[30][31][32] Our results are also in agreement with the available experimental results. [33][34][35][36][37][38][39][40][41][42] The transition state is predicted to have an imaginary vibrational frequency of 1327i cm −1 (cc-pVDZ) or 1235i cm −1 (cc-pVTZ), and the corresponding normal mode reveals simultaneous Cl-H4 bond breaking and O2-H4 bond formation as the reaction proceeds toward Cl + (H 2 O) 2 .…”

Section: Resultsmentioning

confidence: 99%

The exothermic HCl + OH·(H2O) reaction: Removal of the HCl + OH barrier by a single water molecule

Wang

et al. 2014

The Journal of Chemical Physics

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The entrance complex, transition state, and exit complex for the title reaction have been investigated using the CCSD(T) method with correlation consistent basis sets up to cc-pVQZ. The stationary point geometries for the reaction are related to but different from those for the water monomer reaction HCl + OH → Cl + H2O. Our most important conclusion is that the hydrogen-bonded water molecule removes the classical barrier entirely. For the endothermic reverse reaction Cl + (H2O)2, the second water molecule lowers the relative energies of the entrance complex, transition state, and exit complex by about 4 kcal/mol. The title reaction is exothermic by 17.7 kcal/mol. The entrance complex HCl⋯OH·(H2O) is bound by 6.9 kcal/mol relative to the separated reactants. The classical barrier height for the reverse reaction is predicted to be 16.5 kcal/mol. The exit complex Cl⋯(H2O)2 is found to lie 6.8 kcal/mol below the separated products. The potential energy surface for the Cl + (H2O)2 reaction is radically different from that for the valence isoelectronic F + (H2O)2 system.

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“…44,45 The peaks at 3213 and 1400 cm −1 correspond to hydroxyl groups, and the peak at 1100 cm −1 is associated with the stretching vibration of O−H. 46 The PNP solution was evaporated, yielding a yellow powder. The product was then dissolved in D 2 O.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Diverse States and Properties of Polymer Nanoparticles and Gel Formed by Polyethyleneimine and Aldehydes and Analytical Applications

Qü

Zhou

et al. 2015

Anal. Chem.

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Multicolor polymer nanoparticles (or dots) were prepared via the reaction between hyperbranched polyethyleneimine (PEI) and aldehydes, and when the concentration of aldehydes was lower, the final mixture displayed gelation behavior. This phenomenon can be applied to visual detection of aldehydes. Moreover, the colors of the polymer dots and gel are varied by using different kinds of aldehydes, which can be utilized for visual discrimination of aldehydes. For simplicity, we focus our attention on the interaction between PEI and formaldehyde. The nanoparticles show an average diameter of 42 nm, emit bright cyan fluorescence with high quantum yield, and exhibit high water dispersibility and excellent photostability. Due to the advantages, our polymer nanoparticles (PNPs) are utilized as a fluorescent probe for imaging in living SK-N-SH cells. Furthermore, valuable explorations have been carried out on the fundamental properties of PNPs, such as concentration-dependent fluorescence, pH-dependent fluorescence, and solvent effect.

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Infrared Spectroscopy and Quantum Chemical Calculations of OH-(H₂O)_n Complexes

Cited by 50 publications

References 28 publications

The Reaction between Bromine and the Water Dimer and the Highly Exothermic Reverse Reaction

The Reaction between Bromine and the Water Dimer and the Highly Exothermic Reverse Reaction

The exothermic HCl + OH·(H2O) reaction: Removal of the HCl + OH barrier by a single water molecule

Diverse States and Properties of Polymer Nanoparticles and Gel Formed by Polyethyleneimine and Aldehydes and Analytical Applications

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