Rotational and electronic anisotropy in no X2Π from the photodissociation of CH3ONO

Lahmani, F.; Lardeux, C.; Solgadi, D.

doi:10.1016/0009-2614(86)80162-2

Cited by 69 publications

(21 citation statements)

References 13 publications

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“…4'23 Our data confirm this trend, as can be seen from the fitted Gaussian curves in Figure 2a, but this figure also shows that the ratios A"/A' could be explicitly measured for a limited number of J" values. For both g2 1/2 and 3/2 these ratios at high J" were found to be considerably larger than those measured for 355 nm photolysis by Lahmani et al, 4 and closer to the limit expected for complete electron alignment. 23 For example, at J" 36.5, the present results show A"/A' 2.7 for I'I1/2, 3.7 for 1-I3/2 compared to values of 2.0 and 2.7 respectively reported by Lahmani et al., 4 and a complete alignment value of 5.8.…”

Section: (C) Lambda Doublet Ratiossupporting

confidence: 41%

“…For both g2 1/2 and 3/2 these ratios at high J" were found to be considerably larger than those measured for 355 nm photolysis by Lahmani et al, 4 and closer to the limit expected for complete electron alignment. 23 For example, at J" 36.5, the present results show A"/A' 2.7 for I'I1/2, 3.7 for 1-I3/2 compared to values of 2.0 and 2.7 respectively reported by Lahmani et al., 4 and a complete alignment value of 5.8. 23 The reason for the differences in the two sets of experimental results is not clear.…”

Section: (C) Lambda Doublet Ratiossupporting

confidence: 41%

“…The second of these, the study of "dynamical stereochemistry" in photodissociation has recently become a topic of considerable interest. The experimental technique which has made the largest impact in this field is that of tunable laser induced fluorescence (LIF) detection of the fragments, and this has enabled a variety of vector correlations to be measured in diatomic photofragments such as OH(X21I), 2'3 NO(XII), [4][5][6][7][8][9] CN(XE+) 10 and CO(Xl +). 11 This report is of LIF measurements of scalar and vector properties of the NO(X2II) product of the 355 nm photodissociation of methyl…”

Section: Introductionmentioning

confidence: 99%

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The 355 nm Photolysis of Methyl Nitrite

Atkins¹,

Hancock²

1988

Laser Chemistry

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Single photon laser induced fluorescence (LIF) has been used to study the NO fragment produced in its ground electronic state from the 355 nm photolysis of CH3ONO. Populations of rotational, vibrational, spin-orbit and lambda doublet components have been measured. The results are in broad agreement with previous two photon LIF studies, and confirm the dynamics of the process in which the NO fragment departs from an essentially planar CONO framework with non-statistical energy partitioning in the internal states of the products.

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Section: (C) Lambda Doublet Ratiossupporting

confidence: 41%

Section: (C) Lambda Doublet Ratiossupporting

confidence: 41%

Section: Introductionmentioning

confidence: 99%

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The 355 nm Photolysis of Methyl Nitrite

Atkins¹,

Hancock²

1988

Laser Chemistry

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“…2 The primary dissociation pathway associated with the two UV absorption bands was found to be due to the cleavage of the weak RO-NO bond ͑ϳ170 kJ/ mol͒. 8 While extensive studies have been performed on nitrous acid ͑HONO͒, [3][4][5][9][10][11] methyl nitrite ͑CH 3 ONO͒, 6,7,[12][13][14][15] and tert-butyl nitrite ͑͑CH 3 ͒ 3 CONO͒, 7,16-19 there remains quite meager in the photodissociation studies on n-butyl nitrite ͑n-C 4 H 9 ONO͒ and isoamyl nitrite ͑͑CH 3 ͒ 2 C 3 H 5 ONO͒. To the best of our knowledge, only two recent works on the photodissociation dynamics of n-C 4 H 9 ONO were reported by Yue et al, 2,20 who measured the nascent NO ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

Photolysis of n-butyl nitrite and isoamyl nitrite at 355 nm: A time-resolved Fourier transform infrared emission spectroscopy and ab initio study

Jiang

Zhang

et al. 2009

The Journal of Chemical Physics

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We report on the photodissociation dynamics study of n-butyl nitrite and isoamyl nitrite by means of time-resolved Fourier transform infrared (TR-FTIR) emission spectroscopy. The obtained TR-FTIR emission spectra of the nascent NO fragments produced in the 355 nm laser photolysis of the two alkyl nitrite species showed an almost identical rotational temperature and vibrational distributions of NO. In addition, a close resemblance between the two species was also found in the measured temporal profiles of the IR emission of NO and the recorded UV absorption spectra. The experimental results are consistent with our ab initio calculations using the time-dependent density functional theory at the B3LYP/6-311G(d,p) level, which indicate that the substitution of one of the two gamma-H atoms in n-C(4)H(9)ONO with a methyl group to form (CH(3))(2)C(3)H(5)ONO has only a minor effect on the photodissociation dynamics of the two molecules.

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“…[15][16][17] However, it has been confirmed by photofragment yield experiments that detect the NO fragment and must be considered as valid. 19,20 Two groups, one in Orsay 3,5, 6 and one in Zürich 7,8,10,12,13,18 have brought the experimental evidence that the dissociation of CH 3 ONO following the S 1 ←S 0 excitation is indirect, and proceeds according to a vibrational predissociation. The group in Zürich has estimated, indirectly, the dissociation time of the molecules 8,12 : a vector correlation experiment was used to measure both the anisotropy parameter ␤ of the angular distribution and the rotational alignment of the NO fragment for the individual vibrational levels vЉϭ0, 1 and 2 of the NO fragment.…”

Section: Introductionmentioning

confidence: 99%

Observation of an indirect pathway in the femtosecond study of alkyl nitrite photodissociation in the S1 state

Mestdagh

Berdah

Dimicoli

et al. 1995

The Journal of Chemical Physics

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The present work has addressed the question of the dissociation time of four alkyl nitrites upon photoexcitation in the S 1 state ͑methyl nitrite, n-, and t-butyl nitrites and i-amyl nitrite͒. The time resolved Laser Induced Fluorescence technique has been used in the femtosecond regime under bulk conditions. The photodissociation has been initiated at 351 nm by 150 fs pump pulses, and has been probed using a two-photon process at 467 nm by 200 fs pulses. The LIF signal has qualitatively the same shape for the four nitrites: it passes through a transient peak before reaching a plateau. The two-photon process that induces the detected fluorescence is nonresonant for detection of the dissociation product NO through the A←X transition. Conversely, the two-photon process is resonant or quasiresonant for detection of the excited nitrite molecule in the S 1 level before it dissociates. This leads to an enhanced detection efficiency of the non-dissociated excited molecule versus that of the NO fragment. A simple kinetic model has been developed to account for this detection scheme. It shows that the transient peak is observable only if the lifetime of the excited molecule is comparable or larger than the temporal width of the lasers. In that case, the model allows the determination of an effective lifetime of the excited molecule from the measured LIF signal. Lifetimes have been found in the range of 125 fs for the four nitrites investigated. This has allowed us to answer a controversy on the dissociation mechanism of methyl nitrite and to confirm that an indirect pathway exists in the photodissociation of this molecule.

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Rotational and electronic anisotropy in no X2Π from the photodissociation of CH3ONO

Cited by 69 publications

References 13 publications

The 355 nm Photolysis of Methyl Nitrite

The 355 nm Photolysis of Methyl Nitrite

Photolysis of n-butyl nitrite and isoamyl nitrite at 355 nm: A time-resolved Fourier transform infrared emission spectroscopy and ab initio study

Observation of an indirect pathway in the femtosecond study of alkyl nitrite photodissociation in the S1 state

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