The vibrational spectra of ethylene monomer and dimer in argon matrices

Cowieson, D. R.; Barnes, Austin J.; Orville-Thomas, W.J.

doi:10.1002/jrs.1250100144

Cited by 31 publications

(26 citation statements)

References 6 publications

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“…In the following, to help recognize how the ethylene modes change upon adsorption, we keep the symmetry notation of the isolated ethylene ( D 2 h point group). The vibrational frequencies computed in the gas phase are close to the corresponding experimental values . Upon adsorption, most of the vibrational frequencies are downshifted.…”

Section: Introductionsupporting

confidence: 76%

First‐Principles Simulation of Raman Spectra of Adsorbates on Metal Surfaces

2017

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A general method is proposed to simulate the Raman spectra of adsorbates on metal surfaces. This method is based on an electrostatic‐corrected cluster model with additional charges to compensate the loss of coordination of metal atoms, and an external field added to simulate the surface dipole and to reproduce the charge distribution obtained from periodic calculations. As a result, it is possible to couple the phonon calculation with the Raman tensors computed by this corrected cluster model to simulate the Raman spectra of the adsorbates on metal surfaces. In doing so, it is possible to overcome both the infinite dielectric constant of the ideal metal, which makes calculating Raman spectra with current periodic models impossible, and the inaccuracy in adsorbate–metal interactions described by the cluster model. By means of this method, the relative experimental Raman intensity peaks of ethylene adsorbed on metal surfaces were successfully reproduced. Moreover, the model analysis allowed relating the enhancement of the Raman intensity of both CO and ethylene upon chemisorption on the metal surface to both the gain of charges on C atoms and the polarization of orbitals. As such, the proposed method provides an accurate and efficient way to simulate and interpret Raman spectra of adsorbates on metal surfaces.

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Section: Introductionsupporting

confidence: 76%

First‐Principles Simulation of Raman Spectra of Adsorbates on Metal Surfaces

2017

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“…Vibrational frequencies for monomer ethylene and for the dimer of orientation K were calculated at the HF/6-311G* level. 33 The calculations show that the shifts of the frequencies and the changes of the intensities are small. The comparison shows that many fundamentals exhibit slight red shifts.…”

Section: Resultsmentioning

confidence: 94%

“…Rytter and Grued2 and Cowieson et al 33 have reported the analysis of IR spectra of ethylene dimer in an Ar matrix. The structure of ethylene dimer is still a controversial issue, as mentioned in the Introduction.…”

Section: Resultsmentioning

confidence: 99%

Nonbonding interaction potential of ethylene dimer obtained from ab initio molecular orbital calculations: prediction of a D2d structure

Tsuzuki¹,

Tanabe²

1992

J. Phys. Chem.

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“…From IR spectra of the etylene dimer in Ar matrix, Rytter et al [35] and Cowieson et al [36] proposed that structure of the etylene dimer has D2a symmetry. This is consistent with the experimental measurement of the dipole moment of the etylene dimer which predicted a nonpolar system [37].…”

Section: Iii3 Etylene Dimermentioning

confidence: 99%

Intermolecular interactions: basis set and intramolecular correlation effects on semiempirical methods. Application to (C2H2)2, (C2H2)3 and (C2H4)2

Brenner

Millié

1994

Z Phys D - Atoms, Molecules and Clusters

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Abstract.A detailed study of the intrinsic consistency of the semiempirical method of P. Claverie namely, the effects of the basis set and intramolecular correlation on the multipole distributions of molecular subunits and the influence of the electronic population of each atom in the molecular subunit on its van der Waals radius, is performed on some van der Waals dimers. The validity, limits of this model and the appropriate way to use it is established. In particular, the dependence of the geometry and the interaction energy on the basis set chosen and the intramolecutar correlation shows that the multipole distribution involved in the calculation of the electrostatic and polarization terms must be derived from a correlated wave function within an extended basis set. Associated to non local methods for finding stationary points, the method of P. Claverie reproduce reliably the intermolecular geometrical parameters observed for the equilibrium structures and the transition states of the dimer and trimer of acetylene. In addition, a study of the equilibrium structures of the ethylene dimer is presented, the aim of being to clarify the considerable uncertainty in their number and their geometry.

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The vibrational spectra of ethylene monomer and dimer in argon matrices

Abstract: Raman spectra of ethylene trapped in argon matrices are compared with the corresponding infrared data. Bands due to monomer and dimer species could be distinguished by their concentration dependence. Possible structures of the dimer are discussed.

Cited by 31 publications

References 6 publications

First‐Principles Simulation of Raman Spectra of Adsorbates on Metal Surfaces

First‐Principles Simulation of Raman Spectra of Adsorbates on Metal Surfaces

Nonbonding interaction potential of ethylene dimer obtained from ab initio molecular orbital calculations: prediction of a D2d structure

Intermolecular interactions: basis set and intramolecular correlation effects on semiempirical methods. Application to (C2H2)2, (C2H2)3 and (C2H4)2

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