The role of near-resonant intermediate states in the two-photon excitation of nitrogen dioxide: the distinct dynamics of two-photon photofragmentation

Bigio, Laurence; Tapper, Rochelle S.; Grant, Edward R.

doi:10.1021/j150651a002

Cited by 38 publications

(9 citation statements)

References 3 publications

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“…The observation of vibrational inversion in the diatomic cofragments is in accord with previous work. 113 Our results were also recently confirmed by Schmaunz et al in an elegant variation of the VMI experiment. 114 From the multipole moments obtained from the O( 1 D 2 ) images we concluded that the majority of these fragments are formed in the M J = AE1 magnetic sublevels and that all of the O( 1 D 2 ) fragments are produced via the same avoided crossing to the (4) 2 A 0 dissociative electronic state.…”

Section: Valence-valence Transitionssupporting

confidence: 89%

“…A subsequent publication compared these results with the single photon photoproduct distributions formed on excitation to the (2) 2 B 2 state. 113 The single and two photon distributions were observed to be markedly different.…”

Section: Valence-valence Transitionsmentioning

confidence: 97%

“…Later studies by Grant and co-workers used multiphoton excitation processes to probe the same Rydberg series by monitoring the parent ionisation occurring after resonant transitions through the (1) 2 B 2 first excited state and the low-lying 3p Rydberg levels. 113,[130][131][132][133] After single photon excitation to the (1) 2 B 2 manifold, the interconversion that occurs to vibrationally excited levels of the (1) 2 A 1 state results in many nuclear geometries being sampled. This provides access to low-lying vibrational levels of the linear Rydberg series which have poor Franck-Condon overlap for single photon transitions from the bent electronic ground state.…”

Section: Valence-valence Transitionsmentioning

confidence: 99%

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Some remarks on the photodynamics of NO2

Wilkinson

Whitaker

2010

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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We review the literature concerning the electronic structure and spectroscopy of nitrogen dioxide for excitation energies up to 20 eV. Our aim is not to be exhaustive but rather to summarize important results and observations which we have found useful in the interpretation of recent experiments in both the frequency and time domain in which competing and often multiphoton excitation paths access high lying Rydberg and valence states. The photodynamics in NO 2 are particularly fascinating and complicated by numerous non-adiabatic couplings between the various electronic states which, despite the molecule's apparent simplicity as a triatomic species, leads to a very rich photochemistry that exemplifies many features occurring in the photochemistry of much larger molecules.

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Section: Valence-valence Transitionssupporting

confidence: 89%

Section: Valence-valence Transitionsmentioning

confidence: 97%

Section: Valence-valence Transitionsmentioning

confidence: 99%

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Some remarks on the photodynamics of NO2

Wilkinson

Whitaker

2010

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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“…Second, the low laser fluence employed for the resonant excitation step of NO, which is of the order of only 10 5 W cm 22 , drastically reduces the occurrence of two photon processes needed for the photolysis/excitation sequence. Third, if photolytically generated, it is very likely that the neutral NO photofragment is distributed over a range of vibrational states, as has been shown for NO 2 as precursor, 30 resulting in low fragment signal intensities.…”

Section: Broad-bandwidth Versus Narrow-bandwidth Rempi Of Nomentioning

confidence: 99%

Selective ultra-trace detection of NO and NO2 in complex gas mixtures using broad-bandwidth REMPI mass spectrometry

McKeachie

Veer

Short

et al. 2001

Analyst

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In this paper we demonstrate the feasibility of ultra-trace resonance enhanced multiphoton ionization (REMPI) detection employing a small broad-bandwidth solid state laser system. The results reported here are compared with measurements carried out with a conventional excimer pumped dye laser combination. Mass selected broad-bandwidth REMPI spectra for the environmentally relevant nitrogen oxides NO and NO2 are presented. Tunable broad-bandwidth laser radiation with a spectral resolution of > 10 cm(-1) in the wavelength range 560-400 nm was employed for the detection of NO2. For NO detection, the range 230-224 nm was covered. Laser radiation was generated using an optical parametric oscillator pumped by an unseeded Nd:YAG laser. A mobile time-of-flight mass spectrometer equipped with an atmospheric pressure laser ionization source allowed for mass selective parent ion detection at m/z 30 for NO and m/z 46 for NO2. The limit of detection was 10 pptV for NO and 20 pptV for NO2. A selectivity of > 2000 for both compounds with respect to N2O5, organic nitrates and NO2 in the case of NO is reported. An improved laser system currently under construction is expected to provide detection limits below pptv mixing ratios for both nitrogen oxides in a 20 s integration interval.

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“…Photodissociation studies beyond the threshold regime have been sparse. These have focussed on recording the internal state distribution of the nascent NO fragment from photolysis at 248 nm utilizing laser-induced fluorescence (LIF) [4] and resonance enhanced multiphoton ionization (REMPI) [5], and photolysis around 226 nm with detection by REMPI [6]. There have also been two reports [7,8] on the fine-structure population distributions of the oxygen atom produced by photolysis over a range of UV wavelengths.…”

Section: Introductionmentioning

confidence: 99%