Abstract
Using first principles calculations we unveil fundamental mechanism of hydrolysis reactions of two hazardous chemicals PCl3 and POCl3 with explicit molecular water clusters nearby. It is found that the water molecules play a key role as a catalyst significantly lowing activation barrier of the hydrolysis via transferring its protons to reaction intermediates. Interestingly, torsional angle of the molecular complex at transition state is identified as a vital descriptor on the reaction rate. Analysis of charge distribution over the complex further reinforces the finding with atomic level correlation between the torsional angle and variation of the orbital hybridization state of phosphorus (P) in the complex. Electronic charge separation (or polarization) enhances thermodynamic stability of the activated complex and reduces the activation energy through hydrogen bonding network with water molecules nearby. Calculated potential energy surfaces (PES) for the hydrolysis of PCl3 and POCl3 depict their two contrastingly different profiles of double- and triple-depth wells, respectively. It is ascribed to the unique double-bonding O = P in the POCl3. Our results on the activation free energy show well agreements with previous experimental data within 7 kcal mol−1 deviation.
| Original language | English |
|---|---|
| Pages (from-to) | 457-463 |
| Number of pages | 7 |
| Journal | Journal of Hazardous Materials |
| Volume | 341 |
| DOIs | |
| Publication status | Published - 2018 Jan 1 |
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All Science Journal Classification (ASJC) codes
- Environmental Engineering
- Environmental Chemistry
- Waste Management and Disposal
- Pollution
- Health, Toxicology and Mutagenesis
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First principles computational study on hydrolysis of hazardous chemicals phosphorus trichloride and oxychloride (PCl3 and POCl3) catalyzed by molecular water clusters. / Jung, Hyunwook; Kang, Joonhee; Chun, Hoje; Han, Byungchan.
In: Journal of Hazardous Materials, Vol. 341, 01.01.2018, p. 457-463.Research output: Contribution to journal › Article
TY - JOUR
T1 - First principles computational study on hydrolysis of hazardous chemicals phosphorus trichloride and oxychloride (PCl3 and POCl3) catalyzed by molecular water clusters
AU - Jung, Hyunwook
AU - Kang, Joonhee
AU - Chun, Hoje
AU - Han, Byungchan
PY - 2018/1/1
Y1 - 2018/1/1
N2 - Using first principles calculations we unveil fundamental mechanism of hydrolysis reactions of two hazardous chemicals PCl3 and POCl3 with explicit molecular water clusters nearby. It is found that the water molecules play a key role as a catalyst significantly lowing activation barrier of the hydrolysis via transferring its protons to reaction intermediates. Interestingly, torsional angle of the molecular complex at transition state is identified as a vital descriptor on the reaction rate. Analysis of charge distribution over the complex further reinforces the finding with atomic level correlation between the torsional angle and variation of the orbital hybridization state of phosphorus (P) in the complex. Electronic charge separation (or polarization) enhances thermodynamic stability of the activated complex and reduces the activation energy through hydrogen bonding network with water molecules nearby. Calculated potential energy surfaces (PES) for the hydrolysis of PCl3 and POCl3 depict their two contrastingly different profiles of double- and triple-depth wells, respectively. It is ascribed to the unique double-bonding O = P in the POCl3. Our results on the activation free energy show well agreements with previous experimental data within 7 kcal mol−1 deviation.
AB - Using first principles calculations we unveil fundamental mechanism of hydrolysis reactions of two hazardous chemicals PCl3 and POCl3 with explicit molecular water clusters nearby. It is found that the water molecules play a key role as a catalyst significantly lowing activation barrier of the hydrolysis via transferring its protons to reaction intermediates. Interestingly, torsional angle of the molecular complex at transition state is identified as a vital descriptor on the reaction rate. Analysis of charge distribution over the complex further reinforces the finding with atomic level correlation between the torsional angle and variation of the orbital hybridization state of phosphorus (P) in the complex. Electronic charge separation (or polarization) enhances thermodynamic stability of the activated complex and reduces the activation energy through hydrogen bonding network with water molecules nearby. Calculated potential energy surfaces (PES) for the hydrolysis of PCl3 and POCl3 depict their two contrastingly different profiles of double- and triple-depth wells, respectively. It is ascribed to the unique double-bonding O = P in the POCl3. Our results on the activation free energy show well agreements with previous experimental data within 7 kcal mol−1 deviation.
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U2 - 10.1016/j.jhazmat.2017.08.054
DO - 10.1016/j.jhazmat.2017.08.054
M3 - Article
AN - SCOPUS:85028314218
VL - 341
SP - 457
EP - 463
JO - Journal of Hazardous Materials
JF - Journal of Hazardous Materials
SN - 0304-3894
ER -