Very large amplitude intermolecular vibrations and wave function delocalization in 2,3-dimethylnaphthalene · He van der Waals complex

Andreas Bach, Samuel Leutwyler, Dubravko Sabo, Zlatko Bacic

Research output: Contribution to journalArticle

Abstract

We report a combined experimental and theoretical study of the intermolecular vibrations and van der Waals isomerism of the 2,3-dimethylnaphthalene-He van der Waals complex. Two-color resonant two-photon ionization spectra of the S0→S1 electronic transition of 2,3-dimethylnaphthalene-He exhibit five bands within 30 cm -1 of the electronic origin. The intermolecular potential energy surface was modeled as a sum of atom-atom Lennard-Jones pair potentials; it exhibits two equivalent global minima on each side of the naphthalene moiety, and a single shallower local minimum adjacent to the two methyl groups. Based on this surface, accurate three-dimensional quantum calculations of the van der Waals vibrational levels using the discrete variable representation method were performed. Careful optimization of the potential parameters lead to a quantitative reproduction of four observed bands as intermolecular vibrational excitations, a vibrationally averaged He atom distance from the aromatic plane 〈z0〉 = 3.22 Å, and a dissociation energy D0(S1)= -60.3 cm -1, compatible with experiments. The fifth band is assigned as a van der Waals isomer, corresponding to the local minimum. The quantum calculations were extended up to the dissociation limit, yielding ≈ 173 van der Waals vibrational states. Above 70% of D0, many vibrational states are completely delocalized over the potential surface, with root-mean-square vibrational amplitudes up to 6 A parallel to and up to 1.5 A perpendicular to the molecular surface. Calculated tunnelling splittings range from < 10 -4 cm -1 for localized states, to >3 cm -1 for highly delocalized ones.

Original languageEnglish (US)
Pages (from-to)8781-8793
Number of pages13
JournalJournal of Chemical Physics
Volume107
Issue number21
StatePublished - Dec 1 1997

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Wave functions
wave functions
Atoms
vibration
vibrational states
Lennard-Jones potential
Potential energy surfaces
dissociation
atoms
Isomers
Ionization
Photons
electronics
naphthalene
Color
isomers
potential energy
color
ionization
optimization

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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Very large amplitude intermolecular vibrations and wave function delocalization in 2,3-dimethylnaphthalene · He van der Waals complex. / Bach, Andreas; Leutwyler, Samuel; Sabo, Dubravko; Bacic, Zlatko.

In: Journal of Chemical Physics, Vol. 107, No. 21, 01.12.1997, p. 8781-8793.

Research output: Contribution to journalArticle

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abstract = "We report a combined experimental and theoretical study of the intermolecular vibrations and van der Waals isomerism of the 2,3-dimethylnaphthalene-He van der Waals complex. Two-color resonant two-photon ionization spectra of the S0→S1 electronic transition of 2,3-dimethylnaphthalene-He exhibit five bands within 30 cm -1 of the electronic origin. The intermolecular potential energy surface was modeled as a sum of atom-atom Lennard-Jones pair potentials; it exhibits two equivalent global minima on each side of the naphthalene moiety, and a single shallower local minimum adjacent to the two methyl groups. Based on this surface, accurate three-dimensional quantum calculations of the van der Waals vibrational levels using the discrete variable representation method were performed. Careful optimization of the potential parameters lead to a quantitative reproduction of four observed bands as intermolecular vibrational excitations, a vibrationally averaged He atom distance from the aromatic plane 〈z0〉 = 3.22 {\AA}, and a dissociation energy D0(S1)= -60.3 cm -1, compatible with experiments. The fifth band is assigned as a van der Waals isomer, corresponding to the local minimum. The quantum calculations were extended up to the dissociation limit, yielding ≈ 173 van der Waals vibrational states. Above 70{\%} of D0, many vibrational states are completely delocalized over the potential surface, with root-mean-square vibrational amplitudes up to 6 A parallel to and up to 1.5 A perpendicular to the molecular surface. Calculated tunnelling splittings range from < 10 -4 cm -1 for localized states, to >3 cm -1 for highly delocalized ones.",
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