Abstract
Adsorption of perchloroethene (PCE), trichloroethene (TCE), and cis-dichloroethene (cis-DCE) on zerovalentiron is investigated using density functional theory (DFT) to evaluate hypotheses concerning the relative reactivity of these compounds on zerovalent iron. Four different chloroethene adsorption modes on the Fe(110) surface were studied using periodic DFT and the generalized gradient approximation (GGA). Of the adsorption sites examined, the atop site, where the chloroethene C=C bond straddles a surface iron atom, was the most energetically favorable site for the adsorption of all three chloroethenes. Electronic structure and property analyses provide an indication of the extent of sp 2-sp 3 hybridization. The strong hybridization of the π-bonding orbital between the chloroethene C=C bond and the iron surface suggests that adsorbed chloroethenes are strongly activated on Fe(110) and are likely precursors for subsequent chloroethene dissociation on the Fe surface. When the effect of solvation is indirectly taken into account in the DFT simulations by considering the hydration energies of chloroethenes in bulkwater, the ordering of the adsorption energies of chloroethenes from the aqueous phase onto Fe(110) is in agreement with experimental observation (PCE > TCE > cis-DCE). Electronic properties of the adsorbed configurations of chloroethenes are also presented.
| Original language | English |
|---|---|
| Pages (from-to) | 1192-1198 |
| Number of pages | 7 |
| Journal | Environmental Science and Technology |
| Volume | 43 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - 2009 Feb 15 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
- Environmental Chemistry
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Density functional theory studies of chloroethene adsorption on zerovalent lron. / Lim, Dong Hee; Lastoskie, Christian M.; Soon, Aloysius; Becker, Udo.
In: Environmental Science and Technology, Vol. 43, No. 4, 15.02.2009, p. 1192-1198.Research output: Contribution to journal › Article
TY - JOUR
T1 - Density functional theory studies of chloroethene adsorption on zerovalent lron
AU - Lim, Dong Hee
AU - Lastoskie, Christian M.
AU - Soon, Aloysius
AU - Becker, Udo
PY - 2009/2/15
Y1 - 2009/2/15
N2 - Adsorption of perchloroethene (PCE), trichloroethene (TCE), and cis-dichloroethene (cis-DCE) on zerovalentiron is investigated using density functional theory (DFT) to evaluate hypotheses concerning the relative reactivity of these compounds on zerovalent iron. Four different chloroethene adsorption modes on the Fe(110) surface were studied using periodic DFT and the generalized gradient approximation (GGA). Of the adsorption sites examined, the atop site, where the chloroethene C=C bond straddles a surface iron atom, was the most energetically favorable site for the adsorption of all three chloroethenes. Electronic structure and property analyses provide an indication of the extent of sp 2-sp 3 hybridization. The strong hybridization of the π-bonding orbital between the chloroethene C=C bond and the iron surface suggests that adsorbed chloroethenes are strongly activated on Fe(110) and are likely precursors for subsequent chloroethene dissociation on the Fe surface. When the effect of solvation is indirectly taken into account in the DFT simulations by considering the hydration energies of chloroethenes in bulkwater, the ordering of the adsorption energies of chloroethenes from the aqueous phase onto Fe(110) is in agreement with experimental observation (PCE > TCE > cis-DCE). Electronic properties of the adsorbed configurations of chloroethenes are also presented.
AB - Adsorption of perchloroethene (PCE), trichloroethene (TCE), and cis-dichloroethene (cis-DCE) on zerovalentiron is investigated using density functional theory (DFT) to evaluate hypotheses concerning the relative reactivity of these compounds on zerovalent iron. Four different chloroethene adsorption modes on the Fe(110) surface were studied using periodic DFT and the generalized gradient approximation (GGA). Of the adsorption sites examined, the atop site, where the chloroethene C=C bond straddles a surface iron atom, was the most energetically favorable site for the adsorption of all three chloroethenes. Electronic structure and property analyses provide an indication of the extent of sp 2-sp 3 hybridization. The strong hybridization of the π-bonding orbital between the chloroethene C=C bond and the iron surface suggests that adsorbed chloroethenes are strongly activated on Fe(110) and are likely precursors for subsequent chloroethene dissociation on the Fe surface. When the effect of solvation is indirectly taken into account in the DFT simulations by considering the hydration energies of chloroethenes in bulkwater, the ordering of the adsorption energies of chloroethenes from the aqueous phase onto Fe(110) is in agreement with experimental observation (PCE > TCE > cis-DCE). Electronic properties of the adsorbed configurations of chloroethenes are also presented.
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U2 - 10.1021/es802523a
DO - 10.1021/es802523a
M3 - Article
C2 - 19320179
AN - SCOPUS:64349122541
VL - 43
SP - 1192
EP - 1198
JO - Environmental Science & Technology
JF - Environmental Science & Technology
SN - 0013-936X
IS - 4
ER -