Multi-scale simulation of the thermal desorption of large molecules from solid surfaces

Research output: Chapter in Book/Report/Conference proceedingConference contribution

1 Citation (Scopus)

Abstract

We use molecular-dynamics simulations and importance sampling to obtain transition-state theory rate constants for thermal desorption of an n-alkane series from Pt(111). These simulations indicate that the binding of a large molecule to a solid surface is a complex phenomenon involving many local minima. The existence of local minima invalidates the interpretation of thermal desorption as a single, first-order rate process. Because the number of local minima increases with increasing chain length, n-alkane adsorption becomes increasingly dominated by entropy for longer chains. Consequently, the binding energy increases in a less-than-linear way with increasing chain length. Our results provide a quantitative explanation for results and trends in recent experimental studies.

Original languageEnglish (US)
Title of host publication2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002
EditorsM. Laudon, B. Romanowicz
Pages156-158
Number of pages3
StatePublished - Dec 1 2002
Event2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002 - San Juan, Puerto Rico
Duration: Apr 21 2002Apr 25 2002

Publication series

Name2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002

Other

Other2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002
CountryPuerto Rico
CitySan Juan
Period4/21/024/25/02

Fingerprint

Thermal desorption
Chain length
Paraffins
Importance sampling
Molecules
Binding energy
Molecular dynamics
Rate constants
Entropy
Adsorption
Computer simulation

All Science Journal Classification (ASJC) codes

  • Engineering(all)

Cite this

Fichthorn, K. A., Miron, R. A., & Kulkarni, A. K. (2002). Multi-scale simulation of the thermal desorption of large molecules from solid surfaces. In M. Laudon, & B. Romanowicz (Eds.), 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002 (pp. 156-158). (2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002).
Fichthorn, Kristen Ann ; Miron, R. A. ; Kulkarni, Anil Kamalakant. / Multi-scale simulation of the thermal desorption of large molecules from solid surfaces. 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002. editor / M. Laudon ; B. Romanowicz. 2002. pp. 156-158 (2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002).
@inproceedings{47c51120d5cb4c108f8b6da9ee7107e8,
title = "Multi-scale simulation of the thermal desorption of large molecules from solid surfaces",
abstract = "We use molecular-dynamics simulations and importance sampling to obtain transition-state theory rate constants for thermal desorption of an n-alkane series from Pt(111). These simulations indicate that the binding of a large molecule to a solid surface is a complex phenomenon involving many local minima. The existence of local minima invalidates the interpretation of thermal desorption as a single, first-order rate process. Because the number of local minima increases with increasing chain length, n-alkane adsorption becomes increasingly dominated by entropy for longer chains. Consequently, the binding energy increases in a less-than-linear way with increasing chain length. Our results provide a quantitative explanation for results and trends in recent experimental studies.",
author = "Fichthorn, {Kristen Ann} and Miron, {R. A.} and Kulkarni, {Anil Kamalakant}",
year = "2002",
month = "12",
day = "1",
language = "English (US)",
isbn = "0970827563",
series = "2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002",
pages = "156--158",
editor = "M. Laudon and B. Romanowicz",
booktitle = "2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002",

}

Fichthorn, KA, Miron, RA & Kulkarni, AK 2002, Multi-scale simulation of the thermal desorption of large molecules from solid surfaces. in M Laudon & B Romanowicz (eds), 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002. 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002, pp. 156-158, 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002, San Juan, Puerto Rico, 4/21/02.

Multi-scale simulation of the thermal desorption of large molecules from solid surfaces. / Fichthorn, Kristen Ann; Miron, R. A.; Kulkarni, Anil Kamalakant.

2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002. ed. / M. Laudon; B. Romanowicz. 2002. p. 156-158 (2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002).

Research output: Chapter in Book/Report/Conference proceedingConference contribution

TY - GEN

T1 - Multi-scale simulation of the thermal desorption of large molecules from solid surfaces

AU - Fichthorn, Kristen Ann

AU - Miron, R. A.

AU - Kulkarni, Anil Kamalakant

PY - 2002/12/1

Y1 - 2002/12/1

N2 - We use molecular-dynamics simulations and importance sampling to obtain transition-state theory rate constants for thermal desorption of an n-alkane series from Pt(111). These simulations indicate that the binding of a large molecule to a solid surface is a complex phenomenon involving many local minima. The existence of local minima invalidates the interpretation of thermal desorption as a single, first-order rate process. Because the number of local minima increases with increasing chain length, n-alkane adsorption becomes increasingly dominated by entropy for longer chains. Consequently, the binding energy increases in a less-than-linear way with increasing chain length. Our results provide a quantitative explanation for results and trends in recent experimental studies.

AB - We use molecular-dynamics simulations and importance sampling to obtain transition-state theory rate constants for thermal desorption of an n-alkane series from Pt(111). These simulations indicate that the binding of a large molecule to a solid surface is a complex phenomenon involving many local minima. The existence of local minima invalidates the interpretation of thermal desorption as a single, first-order rate process. Because the number of local minima increases with increasing chain length, n-alkane adsorption becomes increasingly dominated by entropy for longer chains. Consequently, the binding energy increases in a less-than-linear way with increasing chain length. Our results provide a quantitative explanation for results and trends in recent experimental studies.

UR - http://www.scopus.com/inward/record.url?scp=6344262054&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=6344262054&partnerID=8YFLogxK

M3 - Conference contribution

AN - SCOPUS:6344262054

SN - 0970827563

T3 - 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002

SP - 156

EP - 158

BT - 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002

A2 - Laudon, M.

A2 - Romanowicz, B.

ER -

Fichthorn KA, Miron RA, Kulkarni AK. Multi-scale simulation of the thermal desorption of large molecules from solid surfaces. In Laudon M, Romanowicz B, editors, 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002. 2002. p. 156-158. (2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002).