Local Mode Vibrations in Polyatomic Molecules

Halonen, Lauri

doi:10.1002/9780470141632.ch2

Cited by 86 publications

(60 citation statements)

References 294 publications

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“…21,22 This local mode degeneracy is very pronounced; the calculated energies may coincide to eight digits. However, this degeneracy is partially removed when one of the stretching doublets is perturbed by a neighboring state.…”

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confidence: 99%

State-selective spectroscopy of water up to its first dissociation limit

Grechko

Boyarkin

Rizzo

et al. 2009

The Journal of Chemical Physics

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confidence: 99%

State-selective spectroscopy of water up to its first dissociation limit

Grechko

Boyarkin

Rizzo

et al. 2009

The Journal of Chemical Physics

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“…For stretch overtones, vibrational energy is effectively localized in a single bond as a result of the large anharmonicity and weak interbond coupling [32]. In local-mode notation [33], (m, n) ± b, m and n represent quanta of stretch localized in each OH bond in symmetric (+) or asymmetric (−) combinations, and b is the number of quanta of bending vibration. We will refer to (m, 0)…”

Section: Introductionmentioning

confidence: 99%

State-resolved spectroscopy of high vibrational levels of water up to the dissociative continuum

Maksyutenko

Grechko

Rizzo

et al. 2012

Phil. Trans. R. Soc. A.

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We summarize here our experimental studies of the high rovibrational energy levels of water. The use of double-resonance vibrational overtone excitation followed by energy-selective photofragmentation and laser-induced fluorescence detection of OH fragments allowed us to measure previously inaccessible rovibrational energies above the seventh OH-stretch overtone. Extension of the experimental approach to triple-resonance excitation provides access to rovibrational levels via transitions with significant transition dipole moments (mainly OH-stretch overtones) up to the dissociation threshold of the O-H bond. A collisionally assisted excitation scheme enables us to probe vibrations that are not readily accessible via pure laser excitation. Observation of the continuous absorption onset yields a precise value for the O-H bond dissociation threshold, 41 145.94 ± 0.15 cm −1 . Finally, we detect long-lived resonances as sharp peaks in spectra above the dissociation threshold.

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“…In Appendix II, we compare the simple and physically meaningful H 0 + H 2 (2) with what has already been reported in the literature 18 by variational methods. In fact,…”

Section: Statement Of the Problem And Methodsmentioning

confidence: 94%

Calculated absorption and vibrational circular dichroism spectra of fundamental and overtone transitions for a chiral HCCH molecular fragment in the hypothesis of coupled dipoles

2005

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We establish the general behavior of absorption and vibrational circular dichroism spectra (VCD) of a chiral HCCH fragment lacking all symmetry elements; the study is limited to CH-stretching modes, and the Hamiltonian employed is written in terms of normal-mode coordinates and momenta and approximates two different Morse oscillators interacting through a harmonic coupling term; rotational strengths are evaluated within a hypothesis of coupled electric dipoles. Van Vleck contact transformations written in terms of raising and lowering operators are used to calculate spectra up to the manifold Deltav = 4. Three transformations are necessary to obtain fourth-order terms in the relevant operators, namely, the electric and magnetic dipole moments. The dynamics of the system exhibits 1:1 resonance terms in addition to the Darling-Dennison coupling term. We discuss the importance of coupling between CH stretches with respect to differences in their local mechanical characteristics in determining the aspect of the absorption and VCD fundamental and overtone spectra of increasing quantum number.

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Local Mode Vibrations in Polyatomic Molecules

Cited by 86 publications

References 294 publications

State-selective spectroscopy of water up to its first dissociation limit

State-selective spectroscopy of water up to its first dissociation limit

State-resolved spectroscopy of high vibrational levels of water up to the dissociative continuum

Calculated absorption and vibrational circular dichroism spectra of fundamental and overtone transitions for a chiral HCCH molecular fragment in the hypothesis of coupled dipoles

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