The role of near-resonant intermediate states in the two-photon excitation of nitrogen dioxide: origin bands in bent-to-linear transitions

Tapper, Rochelle S.; Whetten, Robert L.; Ezra, Gregory S.; Grant, Edward R.

doi:10.1021/j150651a003

Cited by 33 publications

(11 citation statements)

References 2 publications

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“…On the basis of the equivalence core approximation, the C 1s f 3p Rydberg excited states of CO 2 are approximated as the 6a 1 f 3p Rydberg states of NO 2 . Tapper et al 47 reported that the vibrational frequencies for the ν 1 mode are nearly the same, 174 and 171 meV in the 6a 1 f 3pσ u and 3pπ u Rydberg excited states. This is also inconsistent with the present observation.…”

Section: Resultsmentioning

confidence: 99%

Vibronic Couplings in the C 1s → nsσ_g Rydberg Excited States of CO₂

and¹,

Kosugi²,

Shigemasa³

et al. 1996

J. Phys. Chem.

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Fragment ion yields in the C 1s f Rydberg excitation region of CO 2 were measured in the 90°and 0°d irections relative to the electric vector of the linearly polarized light. The C 1s f ns (n ) 3, 4), npπ and npσ (n ) 3-7), and nd (n ) 3, 4) Rydberg transitions are clearly observed and show some vibrational structures. The dipole-forbidden C 1s(σ g ) f 3sσ g Rydberg transition is the strongest of all the Rydberg transitions, and the ion yield in the 90°direction is dominant. This indicates that the bending vibration is predominantly coupled with the 3sσ g Rydberg state and the intensity-lending dipole-allowed state is a very strong π* resonance, only 2 eV lower than the 3sσ g state. On the other hand, in the 4sσ g Rydberg state the vibronic coupling through the antisymmetric stretching mode is strongly observed in the 0°direction. This is probably because the 4sσ g state approaches another intensity-lending state with Σ u + symmetry and goes away from the π* resonance. The angle-resolved ion-yield technique is very powerful for elucidating the vibronic coupling mechanism.

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Section: Resultsmentioning

confidence: 99%

Vibronic Couplings in the C 1s → nsσ_g Rydberg Excited States of CO₂

and¹,

Kosugi²,

Shigemasa³

et al. 1996

J. Phys. Chem.

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“…Baltzer et al 17 observed the onset of the ionic ground state near 10.3 eV and the center of the band near 11.2 eV, substantially higher than the adiabatic energy of 9.586 eV. 31,32 Grant and co-workers [14][15][16] have used multicolor double-resonant multiphoton excitation with tunable nanosecond lasers to study Rydberg states in NO 2 and the state-selective production of vibrationally excited NO 2 + . This double-resonant scheme makes it possible to prepare low lying vibronic states in the 3p and 3p Rydberg states of NO 2 .…”

Section: A Multiphoton Pathways For Formation Of No 2 + + Ementioning

confidence: 99%

“…This is exactly in the region of vibrationally excited levels of the 3p 2 ⌸ u Rydberg state. 14,15 Further absorption of a second 266.7 nm photon from this Rydberg state will produce NO 2 + ions in coincidence with electrons with a rather narrow kinetic energy distribution due to the similarity of the Rydberg state with the ground state of the NO 2 + ion. This width may be mainly determined by the total energy spread of the multiphoton excitation due to the short femtosecond pulses.…”

Section: 34mentioning

confidence: 99%

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Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

Vredenborg¹,

Roeterdink²,

Janssen³

2008

The Journal of Chemical Physics

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The multiphoton multichannel photodynamics of NO 2 has been studied using femtosecond time-resolved coincidence imaging. A novel photoelectron-photoion coincidence imaging machine was developed at the laboratory in Amsterdam employing velocity map imaging and "slow" charged particle extraction using additional electron and ion optics. The NO 2 photodynamics was studied using a two color pump-probe scheme with femtosecond pulses at 400 and 266 nm. The multiphoton excitation produces both NO 2 + parent ions and NO + fragment ions. Here we mainly present the time dependent photoelectron images in coincidence with NO 2 + or NO + and the ͑NO + , e͒ photoelectron versus fragment ion kinetic energy correlations. The coincidence photoelectron spectra and the correlated energy distributions make it possible to assign the different dissociation pathways involved. Nonadiabatic dynamics between the ground state and the A 2 B 2 state after absorption of a 400 nm photon is reflected in the transient photoelectron spectrum of the NO 2 + parent ion. Furthermore, Rydberg states are believed to be used as "stepping" states responsible for the rather narrow and well-separated photoelectron spectra in the NO 2 + parent ion. Slow statistical and fast direct fragmentation of NO 2 + after prompt photoelectron ejection is observed leading to formation of NO + + O. Fragmentation from both the ground state and the electronically excited a 3 B 2 and b 3 A 2 states of NO 2 + is observed. At short pump probe delay times, the dominant multiphoton pathway for NO + formation is a 3 ϫ 400 nm+ 1 ϫ 266 nm excitation. At long delay times ͑Ͼ500 fs͒ two multiphoton pathways are observed. The dominant pathway is a 1 ϫ 400 nm+ 2 ϫ 266 nm photon excitation giving rise to very slow electrons and ions. A second pathway is a 3 ϫ 400 nm photon absorption to NO 2 Rydberg states followed by dissociation toward neutral electronically and vibrationally excited NO͑A 2 ⌺ , v =1͒ fragments, ionized by one 266 nm photon absorption. As is shown in the present study, even though the pump-probe transients are rather featureless the photoelectron-photoion coincidence images show a complex time varying dynamics in NO 2 . We present the potential of our novel coincidence imaging machine to unravel in unprecedented detail the various competing pathways in femtosecond time-resolved multichannel multiphoton dynamics of molecules.

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“…9 The structure we observed consisted of vibrational progressions that resemble those found at a very similar energy in the (2+1)-photon ionization spectrum of the 3ps 2 Σ u + Rydberg state of NO 2 . 61 By means of ab initio calculations, we estimated the ionization potential of vinoxy to lie close to that of NO 2 . 62 Thus, it seems reasonable to associate this structure with a similar 3p Rydberg orbital built on the CH 2 CHO core.…”

Section: Ionization-detected Two-photon Absorption Spectrum Of Vinoxymentioning

confidence: 96%

Multiresonant Spectroscopy and the High-Resolution Threshold Photoionization of Combustion Free Radicals

Grant¹

2005

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This report describes the results of a program of research on the thermochemistry, spectroscopy and intramolecular relaxation dynamics of the combustion intermediate, HCO. We prepare this radical from acetaldehyde as a photo-precursor in a differentially pumped laser-ionization source quadrupole mass spectrometer. Using a multiresonant spectroscopic technique established in our laboratory, we select individual rotational states and overcome Franck-Condon barriers associated with neutral-to-cation geometry changes to promote transitions to individual autoionizing series and state-resolved ionization thresholds. Systematic analysis of rotational structure and associated lineshapes provide experimental insight on autoionization dynamics as input for theoretical modeling.Extrapolation of series, combined with direct thresholdphotoelectron detection, yield precise ionization potentials that constitute an important contribution to the thermochemical base of information on HCO.

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The role of near-resonant intermediate states in the two-photon excitation of nitrogen dioxide: origin bands in bent-to-linear transitions

Cited by 33 publications

References 2 publications

Vibronic Couplings in the C 1s → nsσ_g Rydberg Excited States of CO₂

Vibronic Couplings in the C 1s → nsσ_g Rydberg Excited States of CO₂

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

Multiresonant Spectroscopy and the High-Resolution Threshold Photoionization of Combustion Free Radicals

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The role of near-resonant intermediate states in the two-photon excitation of nitrogen dioxide: origin bands in bent-to-linear transitions

Cited by 33 publications

References 2 publications

Vibronic Couplings in the C 1s → nsσg Rydberg Excited States of CO2

Vibronic Couplings in the C 1s → nsσg Rydberg Excited States of CO2

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

Multiresonant Spectroscopy and the High-Resolution Threshold Photoionization of Combustion Free Radicals

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Vibronic Couplings in the C 1s → nsσ_g Rydberg Excited States of CO₂

Vibronic Couplings in the C 1s → nsσ_g Rydberg Excited States of CO₂