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Gostein, Michael; Watts, Eleanor; Sitz, Greg O.

doi:10.1103/physrevlett.79.2891

Cited by 53 publications

(39 citation statements)

References 20 publications

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“…Alternatively, such experiments may also yield rotational state populations (as measured for H 2 + Pd(100) 99 ), average translational energies for H 2 desorbing from the surface in particular (v, J) states (as measured for H 2 + Cu(100) 20 ) and initial rotational quadrupole alignment parameters describing the orientational dependence of reaction (measured for, for instance, H 2 + Cu(111), 100-102 H 2 + Cu(100), 20 and H 2 + Pd(100) 103 ). Additional valuable information can perhaps be obtained from experiments that use laser excitation and detection using resonance enhanced multi-photon ionization (REMPI) to determine probabilities for rotationally inelastic scattering, like the experiments performed earlier for H 2 + Cu(111), 104 H 2 , 105 HD, 106 and D 2 107 + Cu(100) and H 2 , 108 HD, 106 and D 2 107 + Pd(111).…”

Section: Scattering and Reaction At Off-normal Incidencementioning

confidence: 99%

The effect of the exchange-correlation functional on H2 dissociation on Ru(0001)

Wijzenbroek¹,

Kroes²

2014

The Journal of Chemical Physics

191

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The specific reaction parameter (SRP) approach to density functional theory (DFT) has enabled a chemically accurate description of reactive scattering experiments for activated H 2 -metal systems (H 2 + Cu(111) and Cu(100)), but its application has not yet resulted in a similarly accurate description of non-activated or weakly activated H 2 -metal systems. In this study, the effect of the choice of the exchange-correlation functional in DFT on the potential energy surface and dynamics of H 2 dissociation on Ru(0001), a weakly activated system, is investigated. In total, full potential energy surfaces were calculated for over 20 different functionals. The functionals investigated include functionals incorporating an approximate description of the van der Waals dispersion in the correlation functional (vdW-DF and vdW-DF2 functionals), as well as the revTPSS meta-GGA. With two of the functionals investigated here, which include vdW-DF and vdW-DF2 correlation, it has been possible to accurately reproduce molecular beam experiments on sticking of H 2 and D 2 , as these functionals yield a reaction probability curve with an appropriate energy width. Diffraction probabilities computed with these two functionals are however too high compared to experimental diffraction probabilities, which are extrapolated from surface temperatures (T s ) ≥ 500 K to 0 K using a Debye-Waller model. Further research is needed to establish whether this constitutes a failure of the two candidate SRP functionals or a failure of the Debye-Waller model, the use of which can perhaps in future be avoided by performing calculations that include the effect of surface atom displacement or motion, and thereby of the experimental T s .

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Section: Scattering and Reaction At Off-normal Incidencementioning

confidence: 99%

The effect of the exchange-correlation functional on H2 dissociation on Ru(0001)

Wijzenbroek¹,

Kroes²

2014

The Journal of Chemical Physics

191

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“…Since the early 1980s, the reactive, the rotationally elastic and inelastic, and the diffractive scattering of molecular hydrogen from metal surfaces have been studied extensively, both experimentally [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] and theoretically. [17][18][19][20][21][22][23][24][25][26][27][28] Much attention has been devoted to HD scattering from Pt͑111͒ because of, inter alia, the high probabilities for rotational excitation to only a limited number of accessible rotational states.…”

Section: Introductionmentioning

confidence: 99%

Diffractive and reactive scattering of (v=0, j=0) HD from Pt(111): Six-dimensional quantum dynamics compared with experiment

Kingma

Somers

Pijper

et al. 2003

The Journal of Chemical Physics

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We present results of (vϭ0, jϭ0) HD reacting on and scattering from Pt͑111͒ at off-normal angles of incidence, treating all six molecular degrees of freedom quantum mechanically. The six-dimensional potential energy surface ͑PES͒ used was obtained from density functional theory, using the generalized gradient approximation and a slab representation of the metal surface. Diffraction and rotational excitation probabilities are compared with experiment for two incidence directions, at normal incidence energies between 0.05-0.16 eV and at a parallel translational energy of 55.5 meV. The computed ratio of specular reflection to nonspecular in-plane diffraction for HDϩPt͑111͒ is lower than found experimentally, and lower for HDϩPt͑111͒ than for H 2 ϩPt(111) for both incidence directions studied. The calculations also show that out-of-plane diffraction is much more efficient than in-plane diffraction, underlining that results from experiments that solely attempt to measure in-plane diffraction are not sufficient to show the absence of surface corrugation. Discrepancies in rotational excitation and diffraction probabilities between theory and experiment are discussed, as well as possible future improvements in the dynamical model and in the calculation of the PES.

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“…Also, rotational excitation has been seen in vibrationally elastic scattering of H 2 incident in ͑y 1, j 0, 1͒ on Cu(111) [7]. Individual transitions in which rotational excitation accompanied vibrational deexcitation were seen in experiments on H 2 1 Pd͑111͒ [19], but in this system an important role is played by the surface degrees of freedom [19]. In contrast, the measured vibrational excitation on Cu is independent of surface temperature [3][4][5].…”

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confidence: 98%

Rotational Effects on Vibrational Excitation ofH2on Cu(100)

et al. 1999

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Previous experiments have shown that vibrational excitation of H 2 on Cu(111) is accompanied by rotational cooling but were unable to resolve the underlying mechanism. Six-dimensional quantum dynamical calculations on scattering of ͑y 0, j͒ H 2 from Cu(100) strongly suggest that the observed cooling is due to rotational deexcitation occurring simultaneously with vibrational excitation. An alternative mechanism, in which vibrational excitation decreases with increasing initial angular momentum j but j itself is conserved, is ruled out with certainty. [S0031-9007(99)

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Vibrational Relaxation ofH2(v=1,J

Cited by 53 publications

References 20 publications

The effect of the exchange-correlation functional on H2 dissociation on Ru(0001)

The effect of the exchange-correlation functional on H2 dissociation on Ru(0001)

Diffractive and reactive scattering of (v=0, j=0) HD from Pt(111): Six-dimensional quantum dynamics compared with experiment

Rotational Effects on Vibrational Excitation ofH2on Cu(100)

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