Density functional theory studies of chloroethene adsorption on zerovalent lron

Dong Hee Lim, Christian M. Lastoskie, Aloysius Soon, Udo Becker

Research output: Contribution to journalArticle

18 Citations (Scopus)

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 languageEnglish
Pages (from-to)1192-1198
Number of pages7
JournalEnvironmental Science and Technology
Volume43
Issue number4
DOIs
Publication statusPublished - 2009 Feb 15

Fingerprint

Density functional theory
adsorption
Adsorption
Trichloroethylene
Iron
trichloroethylene
iron
Electronic properties
Solvation
hydration
Hydration
Electronic structure
energy
Atoms
simulation
electronics

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Lim, Dong Hee ; Lastoskie, Christian M. ; Soon, Aloysius ; Becker, Udo. / Density functional theory studies of chloroethene adsorption on zerovalent lron. In: Environmental Science and Technology. 2009 ; Vol. 43, No. 4. pp. 1192-1198.
@article{04d3971dc1674f5d81070747d422806d,
title = "Density functional theory studies of chloroethene adsorption on zerovalent lron",
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.",
author = "Lim, {Dong Hee} and Lastoskie, {Christian M.} and Aloysius Soon and Udo Becker",
year = "2009",
month = "2",
day = "15",
doi = "10.1021/es802523a",
language = "English",
volume = "43",
pages = "1192--1198",
journal = "Environmental Science & Technology",
issn = "0013-936X",
publisher = "American Chemical Society",
number = "4",

}

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 journalArticle

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.

UR - http://www.scopus.com/inward/record.url?scp=64349122541&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=64349122541&partnerID=8YFLogxK

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 -