Infrared multiphoton dissociation of three nitroalkanes

Wodtke, Alec M.; Hintsa, E. J.; Lee, Yuan T.

doi:10.1021/j100407a019

Cited by 152 publications

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“…They reproduced the experimental branching ratio of Ref. [55] by this pathway. The interesting background and unknown mechanism of NM decomposition encouraged us to do dynamical calculations based on a global potential energy surface (PES) and to undertake state-resolved imaging experiments in parallel.…”

Section: Introductionsupporting

confidence: 80%

“…This large percentage implied efficient isomerization to the nitrite prior to dissociation. The energy barrier for isomerization was estimated to be 55.5 kcal mol −1 , based on the RRKM modeling with some assumptions about the isomerization TS properties [55]. This is about 5 kcal mol −1 lower than the C-N bond fission threshold, therefore, accounting for the significant NO yield.…”

Section: Introductionmentioning

confidence: 99%

“…Nitromethane (NM) is a simple prototype energetic molecule, and its photodissociation dynamics have been studied for many years both in the ultraviolet and via infrared multiphoton dissociation (IRMPD) on the ground electronic state [49][50][51][52][53][54][55]. In the classic paper by Wodtke, Lee and coworkers [55], the IRMPD studies documented two decomposition channels:…”

Section: Introductionmentioning

confidence: 99%

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Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH₃NO₂to CH₃O+NO

Homayoon
¹
,

Bowman
²
,

Dey
³

et al. 2013

Zeitschrift für Physikalische Chemie

6
0
7
0

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Roaming Reaction / Photochemistry / Theoretical Dynamics / Trajectory Calculations / Potential Energy Surfaces / IsomerizationCharacteristic signatures of roaming are seen in the translational energy distribution and rotational energy distributions in the products CH 3 O + NO from the unimolecular dissociation of nitromethane in both theory and experiment. Calculations on a new global potential energy surface reveal the detailed roaming-isomerization dynamics in this process, and these are supported by the experimental observations. Calculations find a characteristic of roaming, namely production of vibrationally excited CH 3 O, which is consistent with experiment. This continues to challenge the conventional idea in transition state theory of a localized transition state bottleneck that is a cornerstone of chemical reaction theory.

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Section: Introductionsupporting
confidence: 80%

Section: Introductionmentioning
confidence: 99%

See 1 more Smart Citation
Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH₃NO₂to CH₃O+NO
Homayoon
¹
,
Bowman
²
,
Dey
³

et al. 2013
Zeitschrift für Physikalische Chemie
6
0
7
0
View full text Add to dashboard Cite
Roaming Reaction / Photochemistry / Theoretical Dynamics / Trajectory Calculations / Potential Energy Surfaces / IsomerizationCharacteristic signatures of roaming are seen in the translational energy distribution and rotational energy distributions in the products CH 3 O + NO from the unimolecular dissociation of nitromethane in both theory and experiment. Calculations on a new global potential energy surface reveal the detailed roaming-isomerization dynamics in this process, and these are supported by the experimental observations. Calculations find a characteristic of roaming, namely production of vibrationally excited CH 3 O, which is consistent with experiment. This continues to challenge the conventional idea in transition state theory of a localized transition state bottleneck that is a cornerstone of chemical reaction theory.
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“…The S C F transition state is reported (8) to be significantly higher in energy than the C-N bond dissociation energy. While the energetics from semiempirical calculations should be interpr~ted with caution, the tight transition state, Cn-N = 1.5 16 A, C -0 1 = 1.584 A, and N -0 1 = 1.299 A, from the M I N D 0 / 3 study of nitro-nitrite rearrangement (6) have been widely quoted (1,12). W e therefore investigated both of the tight transition states reported previously (6,8) using the current MCSCF model to make sure that they do not correspond to another stationary point on the potential energy surface.…”

Section: Discussiorzmentioning
confidence: 99%

Theoretical study of nitro–nitrite rearrangement of CH₃NO₂
Saxon¹,
Yoshimine²
1992
Can. J. Chem.
58
8
38
1
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This paper is dedicated to Professor Sigerzi Hzizinc~gc~ otz the occasion of his 65th birthdayROBERTA P. SAXON and MEGUMU YOSHIMINE. Can. J . Chem. 70, 572 (1992). Calculations designed to characterize the transition state and determine the barrier height for rearrangement of nitromethane to methyl nitrite are reported. Structures of CH,NO,, C H 3 0 N 0 , dissociation products, CH3 + NOz and CH,O + NO, and the transition state for nitro-nitrite rearrangement have been optimized at the MCSCF/4-31G level. The geometry of the transition state may be approximately described as separated CH3 and NO, species with extremely long C-N and C 4 bond lengths, 3.396 and 3.654 A, respectively. Energies have been obtained by large-scale multireference single-and double-excitation CI calculations (6-3 lG:+ basis). The transition state is calculated to lie 56.7 kcal/mol above nitromethane (with zero-point energy). A C-N bond dissociation energy of 51.7 kcal/mol is obtained. Results are compared with the infrared multiphoton dissociation experiment of Wodtke, Hintsa, and Lee.

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“…Using a molecular beam in conjunction with infrared multiphoton dissociation technique, WHL 15,16 suggested an initial isomerization of NMT to MNT when detecting the CH 3 O and NO fragments presumably from the dissociation of the internally very hot, but collision-free, isomerized NMT (cf. eq 3).…”

Section: Introductionmentioning
confidence: 99%

Nitromethane−Methyl Nitrite Rearrangement: A Persistent Discrepancy between Theory and Experiment
Nguyen
¹
,
Le
²
,
Hajgató
³

et al. 2003
J. Phys. Chem. A
69
8
69
0
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We reexamined the mechanism of the unimolecular rearrangement connecting both nitromethane and methyl nitrite isomers. The CH 3 NO 2 potential energy surface was constructed using different molecular orbital [CCSD(T) and CASSCF] and density functional theory (B3LYP) methods including a few lower lying isomeric intermediates. A particular attention has been paid to the two following questions left open by earlier experimental and theoretical studies: (a) does the interconversion between nitromethane and methyl nitrite by a 1,2-CH 3 migration occur via a "loose" or "tight" transition structure (TS)? and (b) is the energy barrier associated with methyl migration actually smaller or larger than the C-N bond dissociation energy? The C-N bond dissociation energy was evaluated with BDE(CH 3 -NO 2 ) ) 60 Phys. Chem. A 2002, 106, 7294), our multiconfigurational CASSCF computations demonstrated that the methyl migration involves a "tight" TS whose electronic wave function is dominated by the Hartree-Fock configuration. Calculations are thus internally consistent indicating that the energy of the TS for 1,2-CH 3 shift is at least 6 kcal/mol above the CH 3 + NO 2 asymptote. Thus, a discrepancy with a previous evaluation of experimental findings (Wodtke, A. M.; Hintsa, E. J.; Lee, Y. T. J. Phys. Chem. 1986, 90, 3549), which placed the CH 3 + NO 2 limit by 5 kcal/mol above the rearrangement TS, appears to persist.

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Infrared multiphoton dissociation of three nitroalkanes

Cited by 152 publications

References 0 publications

Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH₃NO₂to CH₃O+NO

Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH₃NO₂to CH₃O+NO

Theoretical study of nitro–nitrite rearrangement of CH₃NO₂

Nitromethane−Methyl Nitrite Rearrangement: A Persistent Discrepancy between Theory and Experiment

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Infrared multiphoton dissociation of three nitroalkanes

Cited by 152 publications

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Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2to CH3O+NO

Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2to CH3O+NO

Theoretical study of nitro–nitrite rearrangement of CH3NO2

Nitromethane−Methyl Nitrite Rearrangement: A Persistent Discrepancy between Theory and Experiment

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Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH₃NO₂to CH₃O+NO

Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH₃NO₂to CH₃O+NO

Theoretical study of nitro–nitrite rearrangement of CH₃NO₂