Symmetry and rotational orientation effects in dissociative adsorption of diatomic molecules on metals: H2 and HD on Cu(111)

Jiqiong Dai, Jia Sheng, John Zhang

Research output: Contribution to journalArticle

Abstract

Following two previous quantum dynamics studies [J. Chem. Phys. 97, 6784 (1992); 99, 1373 (1993)], we present in this paper a more thorough investigation of the symmetry and rotational orientation effects in dissociative chemisorption of diatomic molecules on metals. Specifically, we extended our theoretical studies to calculate the sticking coefficients for H2 and its isotopomer HD on Cu from all angular momentum states (up to j = 8). Our calculation shows a strong dependence of the dissociation probability P(jm) on both j and m rotation quantum numbers, and the increases of P(jm) are closely correlated with the increase of the quantum number m in a given j manifold. Also the dissociation of the diatomic rotational states whose quantum numbers satisfy j + m = odd is forbidden at low energies for the homonuclear H 2 due to the selection rule. The present study provides further evidence that the effect of diatomic rotation on adsorption mainly arises from the effect of rotational orientation (m dependence) as found in previous studies. This m dependence predicts that at low kinetic energies, the degeneracy-averaged dissociation probability of hydrogen on Cu increases monotonically as the rotation quantum number j increases. However, at high kinetic energies, the adsorption probability first decreases as j increases from 0 to about 4-5 before increasing as j further increases above 4-5. The latter behavior is consistent with a recent experimental measurement by Michelsen et al. of the mean kinetic energy of the rotational states of D2 desorbed from Cu(111).

Original languageEnglish (US)
Pages (from-to)1555-1563
Number of pages9
JournalThe Journal of chemical physics
Volume101
Issue number2
StatePublished - 1994

Fingerprint

diatomic molecules
Kinetic energy
quantum numbers
Metals
Adsorption
Molecules
adsorption
kinetic energy
rotational states
symmetry
dissociation
metals
Angular momentum
Chemisorption
Hydrogen
chemisorption
angular momentum
hydrogen
coefficients
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Symmetry and rotational orientation effects in dissociative adsorption of diatomic molecules on metals : H2 and HD on Cu(111). / Dai, Jiqiong; Sheng, Jia; Zhang, John.

In: The Journal of chemical physics, Vol. 101, No. 2, 1994, p. 1555-1563.

Research output: Contribution to journalArticle

@article{11c93fd7362144178fcffc7a61edf196,
title = "Symmetry and rotational orientation effects in dissociative adsorption of diatomic molecules on metals: H2 and HD on Cu(111)",
abstract = "Following two previous quantum dynamics studies [J. Chem. Phys. 97, 6784 (1992); 99, 1373 (1993)], we present in this paper a more thorough investigation of the symmetry and rotational orientation effects in dissociative chemisorption of diatomic molecules on metals. Specifically, we extended our theoretical studies to calculate the sticking coefficients for H2 and its isotopomer HD on Cu from all angular momentum states (up to j = 8). Our calculation shows a strong dependence of the dissociation probability P(jm) on both j and m rotation quantum numbers, and the increases of P(jm) are closely correlated with the increase of the quantum number m in a given j manifold. Also the dissociation of the diatomic rotational states whose quantum numbers satisfy j + m = odd is forbidden at low energies for the homonuclear H 2 due to the selection rule. The present study provides further evidence that the effect of diatomic rotation on adsorption mainly arises from the effect of rotational orientation (m dependence) as found in previous studies. This m dependence predicts that at low kinetic energies, the degeneracy-averaged dissociation probability of hydrogen on Cu increases monotonically as the rotation quantum number j increases. However, at high kinetic energies, the adsorption probability first decreases as j increases from 0 to about 4-5 before increasing as j further increases above 4-5. The latter behavior is consistent with a recent experimental measurement by Michelsen et al. of the mean kinetic energy of the rotational states of D2 desorbed from Cu(111).",
author = "Jiqiong Dai and Jia Sheng and John Zhang",
year = "1994",
language = "English (US)",
volume = "101",
pages = "1555--1563",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "2",

}

TY - JOUR

T1 - Symmetry and rotational orientation effects in dissociative adsorption of diatomic molecules on metals

T2 - H2 and HD on Cu(111)

AU - Dai, Jiqiong

AU - Sheng, Jia

AU - Zhang, John

PY - 1994

Y1 - 1994

N2 - Following two previous quantum dynamics studies [J. Chem. Phys. 97, 6784 (1992); 99, 1373 (1993)], we present in this paper a more thorough investigation of the symmetry and rotational orientation effects in dissociative chemisorption of diatomic molecules on metals. Specifically, we extended our theoretical studies to calculate the sticking coefficients for H2 and its isotopomer HD on Cu from all angular momentum states (up to j = 8). Our calculation shows a strong dependence of the dissociation probability P(jm) on both j and m rotation quantum numbers, and the increases of P(jm) are closely correlated with the increase of the quantum number m in a given j manifold. Also the dissociation of the diatomic rotational states whose quantum numbers satisfy j + m = odd is forbidden at low energies for the homonuclear H 2 due to the selection rule. The present study provides further evidence that the effect of diatomic rotation on adsorption mainly arises from the effect of rotational orientation (m dependence) as found in previous studies. This m dependence predicts that at low kinetic energies, the degeneracy-averaged dissociation probability of hydrogen on Cu increases monotonically as the rotation quantum number j increases. However, at high kinetic energies, the adsorption probability first decreases as j increases from 0 to about 4-5 before increasing as j further increases above 4-5. The latter behavior is consistent with a recent experimental measurement by Michelsen et al. of the mean kinetic energy of the rotational states of D2 desorbed from Cu(111).

AB - Following two previous quantum dynamics studies [J. Chem. Phys. 97, 6784 (1992); 99, 1373 (1993)], we present in this paper a more thorough investigation of the symmetry and rotational orientation effects in dissociative chemisorption of diatomic molecules on metals. Specifically, we extended our theoretical studies to calculate the sticking coefficients for H2 and its isotopomer HD on Cu from all angular momentum states (up to j = 8). Our calculation shows a strong dependence of the dissociation probability P(jm) on both j and m rotation quantum numbers, and the increases of P(jm) are closely correlated with the increase of the quantum number m in a given j manifold. Also the dissociation of the diatomic rotational states whose quantum numbers satisfy j + m = odd is forbidden at low energies for the homonuclear H 2 due to the selection rule. The present study provides further evidence that the effect of diatomic rotation on adsorption mainly arises from the effect of rotational orientation (m dependence) as found in previous studies. This m dependence predicts that at low kinetic energies, the degeneracy-averaged dissociation probability of hydrogen on Cu increases monotonically as the rotation quantum number j increases. However, at high kinetic energies, the adsorption probability first decreases as j increases from 0 to about 4-5 before increasing as j further increases above 4-5. The latter behavior is consistent with a recent experimental measurement by Michelsen et al. of the mean kinetic energy of the rotational states of D2 desorbed from Cu(111).

UR - http://www.scopus.com/inward/record.url?scp=0001461148&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001461148&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001461148

VL - 101

SP - 1555

EP - 1563

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 2

ER -