H + CD 4 abstraction reaction dynamics: Excitation function and angular distributions

Jon P. Camden, Wenfang Hu, Hans A. Bechtel, Davida J Ankeny Brown, Marion R. Martin, Richard N. Zare, György Lendvay, Diego Troya, George C Schatz

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

We compare experimental photoloc measurements and quasi-classical trajectory calculations of the integral cross sections, lab-frame speed distributions, and angular distributions associated with the CD 3 products of the H + CD 4(v = 0) → CD 3+ HD reaction at collision energies ranging from 0.5 to 3.0 eV. Of the potential energy surfaces (PES) we explored, the direct dynamics calculations using the B3LYP/6-31G** density functional theory PES provide the best agreement with the experimental measurements. This agreement is likely due to the better overall description that B3LYP provides for geometries well removed from the minimum energy path, even though its barrier height is low by ∼0.2 eV. In contrast to previous theoretical calculations, the angular distributions on this surface show behavior associated with a stripping mechanism, even at collision energies only ∼0.1 eV above the reaction barrier. Other potential energy surfaces, which include an analytical potential energy surface from Espinosa-García and a direct dynamics calculation based on the MSINDO semiempirical Hamiltonian, are less accurate and predict more rebound dynamics at these energies than is observed. Reparametrization of the MSINDO surface, though yielding better agreement with the experiment, is not sufficient to capture the observed dynamics. The differences between these surfaces are interpreted using an analysis of the opacity functions, where we find that the wider cone of acceptance on the B3LYP surface plays a crucial role in determining the integral cross sections and angular distributions.

Original languageEnglish
Pages (from-to)677-686
Number of pages10
JournalJournal of Physical Chemistry A
Volume110
Issue number2
DOIs
Publication statusPublished - Jan 19 2006

Fingerprint

Potential energy surfaces
Angular distribution
angular distribution
distribution functions
excitation
potential energy
Hamiltonians
Opacity
Density functional theory
Cones
Trajectories
collisions
Geometry
energy
cross sections
opacity
stripping
acceptability
cones
Experiments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Camden, J. P., Hu, W., Bechtel, H. A., Brown, D. J. A., Martin, M. R., Zare, R. N., ... Schatz, G. C. (2006). H + CD 4 abstraction reaction dynamics: Excitation function and angular distributions. Journal of Physical Chemistry A, 110(2), 677-686. https://doi.org/10.1021/jp053827u

H + CD 4 abstraction reaction dynamics : Excitation function and angular distributions. / Camden, Jon P.; Hu, Wenfang; Bechtel, Hans A.; Brown, Davida J Ankeny; Martin, Marion R.; Zare, Richard N.; Lendvay, György; Troya, Diego; Schatz, George C.

In: Journal of Physical Chemistry A, Vol. 110, No. 2, 19.01.2006, p. 677-686.

Research output: Contribution to journalArticle

Camden, JP, Hu, W, Bechtel, HA, Brown, DJA, Martin, MR, Zare, RN, Lendvay, G, Troya, D & Schatz, GC 2006, 'H + CD 4 abstraction reaction dynamics: Excitation function and angular distributions', Journal of Physical Chemistry A, vol. 110, no. 2, pp. 677-686. https://doi.org/10.1021/jp053827u
Camden, Jon P. ; Hu, Wenfang ; Bechtel, Hans A. ; Brown, Davida J Ankeny ; Martin, Marion R. ; Zare, Richard N. ; Lendvay, György ; Troya, Diego ; Schatz, George C. / H + CD 4 abstraction reaction dynamics : Excitation function and angular distributions. In: Journal of Physical Chemistry A. 2006 ; Vol. 110, No. 2. pp. 677-686.
@article{bbefb39874fa4faf991eadaf0e7861b2,
title = "H + CD 4 abstraction reaction dynamics: Excitation function and angular distributions",
abstract = "We compare experimental photoloc measurements and quasi-classical trajectory calculations of the integral cross sections, lab-frame speed distributions, and angular distributions associated with the CD 3 products of the H + CD 4(v = 0) → CD 3+ HD reaction at collision energies ranging from 0.5 to 3.0 eV. Of the potential energy surfaces (PES) we explored, the direct dynamics calculations using the B3LYP/6-31G** density functional theory PES provide the best agreement with the experimental measurements. This agreement is likely due to the better overall description that B3LYP provides for geometries well removed from the minimum energy path, even though its barrier height is low by ∼0.2 eV. In contrast to previous theoretical calculations, the angular distributions on this surface show behavior associated with a stripping mechanism, even at collision energies only ∼0.1 eV above the reaction barrier. Other potential energy surfaces, which include an analytical potential energy surface from Espinosa-Garc{\'i}a and a direct dynamics calculation based on the MSINDO semiempirical Hamiltonian, are less accurate and predict more rebound dynamics at these energies than is observed. Reparametrization of the MSINDO surface, though yielding better agreement with the experiment, is not sufficient to capture the observed dynamics. The differences between these surfaces are interpreted using an analysis of the opacity functions, where we find that the wider cone of acceptance on the B3LYP surface plays a crucial role in determining the integral cross sections and angular distributions.",
author = "Camden, {Jon P.} and Wenfang Hu and Bechtel, {Hans A.} and Brown, {Davida J Ankeny} and Martin, {Marion R.} and Zare, {Richard N.} and Gy{\"o}rgy Lendvay and Diego Troya and Schatz, {George C}",
year = "2006",
month = "1",
day = "19",
doi = "10.1021/jp053827u",
language = "English",
volume = "110",
pages = "677--686",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - H + CD 4 abstraction reaction dynamics

T2 - Excitation function and angular distributions

AU - Camden, Jon P.

AU - Hu, Wenfang

AU - Bechtel, Hans A.

AU - Brown, Davida J Ankeny

AU - Martin, Marion R.

AU - Zare, Richard N.

AU - Lendvay, György

AU - Troya, Diego

AU - Schatz, George C

PY - 2006/1/19

Y1 - 2006/1/19

N2 - We compare experimental photoloc measurements and quasi-classical trajectory calculations of the integral cross sections, lab-frame speed distributions, and angular distributions associated with the CD 3 products of the H + CD 4(v = 0) → CD 3+ HD reaction at collision energies ranging from 0.5 to 3.0 eV. Of the potential energy surfaces (PES) we explored, the direct dynamics calculations using the B3LYP/6-31G** density functional theory PES provide the best agreement with the experimental measurements. This agreement is likely due to the better overall description that B3LYP provides for geometries well removed from the minimum energy path, even though its barrier height is low by ∼0.2 eV. In contrast to previous theoretical calculations, the angular distributions on this surface show behavior associated with a stripping mechanism, even at collision energies only ∼0.1 eV above the reaction barrier. Other potential energy surfaces, which include an analytical potential energy surface from Espinosa-García and a direct dynamics calculation based on the MSINDO semiempirical Hamiltonian, are less accurate and predict more rebound dynamics at these energies than is observed. Reparametrization of the MSINDO surface, though yielding better agreement with the experiment, is not sufficient to capture the observed dynamics. The differences between these surfaces are interpreted using an analysis of the opacity functions, where we find that the wider cone of acceptance on the B3LYP surface plays a crucial role in determining the integral cross sections and angular distributions.

AB - We compare experimental photoloc measurements and quasi-classical trajectory calculations of the integral cross sections, lab-frame speed distributions, and angular distributions associated with the CD 3 products of the H + CD 4(v = 0) → CD 3+ HD reaction at collision energies ranging from 0.5 to 3.0 eV. Of the potential energy surfaces (PES) we explored, the direct dynamics calculations using the B3LYP/6-31G** density functional theory PES provide the best agreement with the experimental measurements. This agreement is likely due to the better overall description that B3LYP provides for geometries well removed from the minimum energy path, even though its barrier height is low by ∼0.2 eV. In contrast to previous theoretical calculations, the angular distributions on this surface show behavior associated with a stripping mechanism, even at collision energies only ∼0.1 eV above the reaction barrier. Other potential energy surfaces, which include an analytical potential energy surface from Espinosa-García and a direct dynamics calculation based on the MSINDO semiempirical Hamiltonian, are less accurate and predict more rebound dynamics at these energies than is observed. Reparametrization of the MSINDO surface, though yielding better agreement with the experiment, is not sufficient to capture the observed dynamics. The differences between these surfaces are interpreted using an analysis of the opacity functions, where we find that the wider cone of acceptance on the B3LYP surface plays a crucial role in determining the integral cross sections and angular distributions.

UR - http://www.scopus.com/inward/record.url?scp=31544482666&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=31544482666&partnerID=8YFLogxK

U2 - 10.1021/jp053827u

DO - 10.1021/jp053827u

M3 - Article

C2 - 16405340

AN - SCOPUS:31544482666

VL - 110

SP - 677

EP - 686

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 2

ER -