Theoretical studies of the erosion of (100) and (111) diamond surfaces by hyperthermal O(3P)

Jeffrey T. Paci, George C Schatz, Timothy K. Minton

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Direct dynamics simulations, based on density functional-based tight-binding theory with self-consistent charges and also on density functional theory, were used to investigate hyperthermal O(3P) atom collisions with (111) and (100) diamond surfaces. Surface functionalizations produced initially, shortly after the start of oxygen-atom exposure, and during steady-state conditions were investigated. Hydrogen atoms are removed from both surfaces by the incoming oxygen atoms, leading to hydroxyl radicals and water molecules. Both surfaces can be damaged by the incoming oxygen during the initial stages of exposure, resulting in the removal of carbon as CO2 molecules, and functionization of the surfaces with oxygen. The (111) surface is dominated by oxy radicals during steady-state exposure and also has a significant number of carbon atoms with dangling bonds. The (100) surface becomes nearly completely covered by ketone and ether functional groups. Its (2 × 1) reconstruction is opened in the process. Once covered, the (100) surface resists further erosion, presumably because the ether and ketone groups make the surface carbon atoms unattractive to incoming O atoms which act as electrophiles. Two mechanisms exist for the removal of carbon atoms from the (111) surface. The surface can become graphitized by incoming O atom impacts, and graphite is quickly eroded by hyperthermal O atoms. It can also be directly converted to CO2 as a β-scission-like process makes carbon atoms adjacent to oxy radicals susceptible to electrophilic attack.

Original languageEnglish
Pages (from-to)14770-14777
Number of pages8
JournalJournal of Physical Chemistry C
Volume115
Issue number30
DOIs
Publication statusPublished - Aug 4 2011

Fingerprint

Diamond
erosion
Erosion
Diamonds
diamonds
Atoms
Carbon
atoms
carbon
Oxygen
Ketones
ketones
Ether
Ethers
ethers
oxygen atoms
Molecules
Dangling bonds
Graphite
hydroxyl radicals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Theoretical studies of the erosion of (100) and (111) diamond surfaces by hyperthermal O(3P). / Paci, Jeffrey T.; Schatz, George C; Minton, Timothy K.

In: Journal of Physical Chemistry C, Vol. 115, No. 30, 04.08.2011, p. 14770-14777.

Research output: Contribution to journalArticle

@article{fb3193938dd1448190de57c82c31f0c9,
title = "Theoretical studies of the erosion of (100) and (111) diamond surfaces by hyperthermal O(3P)",
abstract = "Direct dynamics simulations, based on density functional-based tight-binding theory with self-consistent charges and also on density functional theory, were used to investigate hyperthermal O(3P) atom collisions with (111) and (100) diamond surfaces. Surface functionalizations produced initially, shortly after the start of oxygen-atom exposure, and during steady-state conditions were investigated. Hydrogen atoms are removed from both surfaces by the incoming oxygen atoms, leading to hydroxyl radicals and water molecules. Both surfaces can be damaged by the incoming oxygen during the initial stages of exposure, resulting in the removal of carbon as CO2 molecules, and functionization of the surfaces with oxygen. The (111) surface is dominated by oxy radicals during steady-state exposure and also has a significant number of carbon atoms with dangling bonds. The (100) surface becomes nearly completely covered by ketone and ether functional groups. Its (2 × 1) reconstruction is opened in the process. Once covered, the (100) surface resists further erosion, presumably because the ether and ketone groups make the surface carbon atoms unattractive to incoming O atoms which act as electrophiles. Two mechanisms exist for the removal of carbon atoms from the (111) surface. The surface can become graphitized by incoming O atom impacts, and graphite is quickly eroded by hyperthermal O atoms. It can also be directly converted to CO2 as a β-scission-like process makes carbon atoms adjacent to oxy radicals susceptible to electrophilic attack.",
author = "Paci, {Jeffrey T.} and Schatz, {George C} and Minton, {Timothy K.}",
year = "2011",
month = "8",
day = "4",
doi = "10.1021/jp201563m",
language = "English",
volume = "115",
pages = "14770--14777",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "30",

}

TY - JOUR

T1 - Theoretical studies of the erosion of (100) and (111) diamond surfaces by hyperthermal O(3P)

AU - Paci, Jeffrey T.

AU - Schatz, George C

AU - Minton, Timothy K.

PY - 2011/8/4

Y1 - 2011/8/4

N2 - Direct dynamics simulations, based on density functional-based tight-binding theory with self-consistent charges and also on density functional theory, were used to investigate hyperthermal O(3P) atom collisions with (111) and (100) diamond surfaces. Surface functionalizations produced initially, shortly after the start of oxygen-atom exposure, and during steady-state conditions were investigated. Hydrogen atoms are removed from both surfaces by the incoming oxygen atoms, leading to hydroxyl radicals and water molecules. Both surfaces can be damaged by the incoming oxygen during the initial stages of exposure, resulting in the removal of carbon as CO2 molecules, and functionization of the surfaces with oxygen. The (111) surface is dominated by oxy radicals during steady-state exposure and also has a significant number of carbon atoms with dangling bonds. The (100) surface becomes nearly completely covered by ketone and ether functional groups. Its (2 × 1) reconstruction is opened in the process. Once covered, the (100) surface resists further erosion, presumably because the ether and ketone groups make the surface carbon atoms unattractive to incoming O atoms which act as electrophiles. Two mechanisms exist for the removal of carbon atoms from the (111) surface. The surface can become graphitized by incoming O atom impacts, and graphite is quickly eroded by hyperthermal O atoms. It can also be directly converted to CO2 as a β-scission-like process makes carbon atoms adjacent to oxy radicals susceptible to electrophilic attack.

AB - Direct dynamics simulations, based on density functional-based tight-binding theory with self-consistent charges and also on density functional theory, were used to investigate hyperthermal O(3P) atom collisions with (111) and (100) diamond surfaces. Surface functionalizations produced initially, shortly after the start of oxygen-atom exposure, and during steady-state conditions were investigated. Hydrogen atoms are removed from both surfaces by the incoming oxygen atoms, leading to hydroxyl radicals and water molecules. Both surfaces can be damaged by the incoming oxygen during the initial stages of exposure, resulting in the removal of carbon as CO2 molecules, and functionization of the surfaces with oxygen. The (111) surface is dominated by oxy radicals during steady-state exposure and also has a significant number of carbon atoms with dangling bonds. The (100) surface becomes nearly completely covered by ketone and ether functional groups. Its (2 × 1) reconstruction is opened in the process. Once covered, the (100) surface resists further erosion, presumably because the ether and ketone groups make the surface carbon atoms unattractive to incoming O atoms which act as electrophiles. Two mechanisms exist for the removal of carbon atoms from the (111) surface. The surface can become graphitized by incoming O atom impacts, and graphite is quickly eroded by hyperthermal O atoms. It can also be directly converted to CO2 as a β-scission-like process makes carbon atoms adjacent to oxy radicals susceptible to electrophilic attack.

UR - http://www.scopus.com/inward/record.url?scp=79961054127&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=79961054127&partnerID=8YFLogxK

U2 - 10.1021/jp201563m

DO - 10.1021/jp201563m

M3 - Article

VL - 115

SP - 14770

EP - 14777

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 30

ER -