The Wavelength Dependence of <i>tert</i>-Butyl Nitrite Surface Photochemistry

Jenniskens, Hans G.; Philippe, L.; Kadodwala, Malcolm; Kleyn, Aart W.

doi:10.1021/jp980325q

Cited by 15 publications

(13 citation statements)

References 48 publications

(92 reference statements)

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“…CH 3 ONO adsorbs weakly and desorbs molecularly, i.e., no thermal dissociation and identifiable monolayer ͑110 to 122 K͒ and multilayer peaks ͑96 -103 K͒. 10,[13][14][15] There is good evidence for two-dimensional ͑2D͒ and 3D islanding, as expected, since the surface of Ag͑111͒ is electronically smooth and since CH 3 ONO has a strong permanent dipole moment.…”

Section: Introductionmentioning

confidence: 91%

“…9,10 Photodissociation of RONO on Ag͑111͒ occurs readily and, surprisingly, there is no evidence for substrate-mediated excitation. [11][12][13] Ag does play a role by aligning the adsorbates and relaxing the nascent NO. In general, NO translational energy distributions exhibit a strong angular dependence and, at each angle, comprise three distinguishable velocity components: fast, intermediate, and slow.…”

Section: Introductionmentioning

confidence: 99%

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Photodissociation of methyl nitrite on Ag(111): Simulation

Kim

White

Agrawal

et al. 2001

The Journal of Chemical Physics

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The photodissociation dynamics of methyl nitrite, CH 3 ONO, on Ag͑111͒ have been simulated using a description that models 61 cis-methyl nitrite molecules adsorbed on a three-layer block of Ag͑111͒. Based on classical intra-and intermolecular potentials and periodic boundary conditions, molecular dynamics ͑MD͒ simulation led to two domain structures at 100 K: those with CONO planes oriented nearly parallel and nearly perpendicular to the Ag͑111͒ surface. To simulate photodissociation dynamics of NO, many NO trajectories were determined, each carried out as follows. At some instant of the MD simulation, a CH 3 ONO molecule was randomly selected from within the group of 61 and its internal CH 3 O-NO bond was stretched to a defined dissociation transition state. The nascent NO was given momentum along the direction of the bond broken and NO translational and internal energies were chosen to match those determined experimentally in collision-free gas phase photodissociation. The motion of the whole adsorbate-substrate system was then calculated while following the trajectory of NO. Analyzing the ensemble of NO trajectories, we conclude that, while the initial orientation of the dissociating CH 3 ONO influences the number of subsequent collisions, the exit direction, and the final translational and internal energy of NO, it does not fully account for the properties of ejected NO. Furthermore, for those molecules lying nearly parallel to the surface, a transition state prepared by simply stretching the ON bond is often located away from the lowest potential energy exit path due to interactions with nearest neighbor species. As a result, coordinates, e.g., internal twisting, other than the internal CH 3 O-NO stretching mode are intimately involved in the dissociation channel.

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Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Photodissociation of methyl nitrite on Ag(111): Simulation

Kim

White

Agrawal

et al. 2001

The Journal of Chemical Physics

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“…Jenniskens and co-workers − examined the 355 and 266 nm photodissociation of TBN on Ag(111). Coverage-dependent bimodal translational energy distributions were observed and fit with the sum of hyperthermal and thermal Boltzmann distributions.…”

Section: Introductionmentioning

confidence: 99%

Photodissociation Dynamics of tert-Butyl Nitrite on Ag(111): Characterization of Translationally and Internally Excited NO Fragments

et al. 2001

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The translational, vibrational, and rotational characteristics of nitric oxide, NO, ejected by 351 nm photodissociation of tert-butyl nitrite, (CH3)3CONO, adsorbed on Ag(111) have been investigated using resonance-enhanced multiphoton ionization time-of-flight (REMPI-TOF) and interpreted using a direct excitation and collisional relaxation model. There are three translational energy components denoted as collisionless, intermediate, and thermalized. The collisionless component has characteristics matching those found for gas phase monomer photolysis. The thermalized component has characteristics expected for NO accommodated to the substrate temperature, while the more complex intermediate component is qualitatively describable in terms of collisions of nascent energetic NO with surrounding species as it exits into the gas phase. There are strong ν‘ ‘ = 1 and 2 but negligible ν‘ ‘ = 0 contributions to the collisionless component. The collisionless component is also characterized by high rotational excitation; Gaussian rotational distributions with J max = 24.5 ± 1 for ν‘ ‘ = 1 and 29.5 ± 1 for ν‘ ‘ = 2 provide reasonable fits. The translationally thermalized component is dominated by the ν‘ ‘ = 0 vibrational state and by a Boltzmann rotational distribution (T rot = 124 ± 30 K); i.e., all three modes of motion are thermalized. The vibrational and rotational characteristics of the intermediate translational component are more complex and will require simulation and angle-resolved REMPI for fuller elucidation.

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“…Alkyl nitrites in the form R-O-N O have many features such as (1) well-defined chromophore, (2) highly sensitive to light, and (3) relatively simple model heteroatom species [11][12][13] and therefore are taken as the ideal probe to the photolysis reactions. For gas-phase photolysis [14][15][16][17][18][19][20][21][22][23], alkyl nitrite can be dissociated into an alkoxy fragment and NO under UV radiation in the following reaction sequence:…”

Section: Introductionmentioning

confidence: 99%