Rotationally resolved ultraviolet-ultraviolet double resonance study of the nonplanar E state of acetylene

In centrosymmetric molecules such as acetylene, one expects one-photon and two-photon spectroscopy to be mutually exclusive by the g↔u electric dipole selection rule. An ultraviolet–ultraviolet double resonance (UVUVDR) spectrum of the 74 000–78 000 cm−1 region of acetylene, recorded using the Ã←X̃...

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Bibliographic Details
Published in:The Journal of chemical physics 1992-11, Vol.97 (10), p.7180-7196
Main Authors: LUNDBERG, J. K, JONAS, D. M, BHAVANI RAJARAM, YONGQIN CHEN, FIELD, R. W
Format: Article
Language:English
Subjects:
Atomic and molecular physics
Exact sciences and technology
Molecular properties and interactions with photons
Multiple resonances (including double and higher-order resonance processes, such as double nuclear magnetic resonance, electron double resonance and microwave optical double resonance)
Physics
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Summary:In centrosymmetric molecules such as acetylene, one expects one-photon and two-photon spectroscopy to be mutually exclusive by the g↔u electric dipole selection rule. An ultraviolet–ultraviolet double resonance (UVUVDR) spectrum of the 74 000–78 000 cm−1 region of acetylene, recorded using the Ã←X̃ transition for the first step in double resonance consists almost entirely of transitions terminating on levels of the Ẽ state identified in one-photon vacuum ultraviolet (vuv) spectroscopy. Evidence for a nonplanar, noncentrosymmetric structure of the Ẽ state obtained by rotationally resolved fluorescence dip detected UVUVDR is presented.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.463543