Rotationally resolved spectroscopy and dynamics of the 3px 1A2 Rydberg state of formaldehyde
| Autor: | Frédéric Merkt, A. M. Schulenburg, Peter Radi, M. Meisinger |
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| Rok vydání: | 2010 |
| Předmět: | |
| Zdroj: | Physical Chemistry Chemical Physics. 12:15592 |
| ISSN: | 1463-9084 1463-9076 |
| DOI: | 10.1039/c0cp00191k |
| Popis: | The rotational structure of the lowest three vibrational levels (0(0), 6(1) and 4(1)) of the 3p(x) (1)A(2) Rydberg state of formaldehyde has been studied by doubly-resonant three-photon ionization spectroscopy. A strong a-type Coriolis interaction between the in-plane rocking (ν(6)) and out-of-plane bending (ν(4)) modes results in the observation of vibronically forbidden transitions to the 6(1) level from the intermediate Ã(1)A(2) (2(1) 4(3)) level. The full widths at half maximum of the rovibronic transitions to the 4(1) state are considerably larger than to the vibrational ground state and the 6(1) level. The band origin (T(0) = 67 728.939(82) cm(-1)), the rigid rotor rotational constants (A = 9.006(19) cm(-1), B = 1.331(20) cm(-1), and C = 1.135(22) cm(-1)), the Coriolis coupling constant (ξ = 8.86(89) cm(-1)) and the deperturbed fundamental wave numbers of both vibrational modes (v[combining tilde](6) = 808.88(25) cm(-1) and v[combining tilde](4) = 984.92(26) cm(-1)) have been determined for the 3p(x) (1)A(2) Rydberg state. Polarization effects originating from the double-resonance technique have been exploited to detect the Coriolis interaction and investigate how it affects the predissociation dynamics. |
| Databáze: | OpenAIRE |
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