State-resolved dynamics of NO produced by photodissociation of t-butyl nitrite on Ag(111)

Kim, C.; Zhao, Wei; White, J. M.

doi:10.1016/s0039-6028(00)00695-6

Cited by 7 publications

(14 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Translational Velocity Distributions. As in our previous 248 nm photolysis study, 35,36 the 351 nm photodissociation of TBN on Ag(111) exhibits trimodal translational distributions (Figure 2), with collisionless (a), intermediate (b), and thermalized (c) components. Bimodal distributions have been reported for photolysis of molecular clusters of TBN 22 and for TBN on MgF 2 .…”

Section: Discussionsupporting

confidence: 78%

“…These three components are attributed to collisionless ejection (a), release after becoming fully thermalized (b), and ejection after one or a few collisions (c). We conclude that, as for 248 nm photolysis, , there is correlation among translational, vibrational, and rotational energies. For example, NO arriving at the detector with little rotational and vibrational energy is also moving slowly, component b, whereas rapidly moving NO, component a, includes negligible amounts of NO in ν‘ ‘ = 0.…”

Section: Resultsmentioning

confidence: 57%

“…The ultrahigh vacuum (UHV) chamber and laser system is described in more detail elsewhere. − Briefly, the experiments were done in a two-level UHV chamber, which operates at a base pressure of < 2 × 10 -10 Torr. An ion gun, reverse-view low-energy electron diffraction (LEED) apparatus, and Auger electron spectrometer comprise the upper level, where the substrate is cleaned and analyzed.…”

Section: Methodsmentioning

confidence: 99%

“…Kim et al 35 investigated the internal state-resolved dynamics of NO produced by 248 nm photodissociation of TBN using REMPI-TOF. For high rotational states (J > 30) the translational energy distribution is dominated by fast, highly nonthermal NO desorption, designated collisionless.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

et al. 2001

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Discussionsupporting

confidence: 78%

Section: Resultsmentioning

confidence: 57%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

et al. 2001

Self Cite

View full text Add to dashboard Cite

show abstract

“…TBN surface photodissociation on Ag(111) by 248 and 351 nm was studied by our group previously. [22][23][24][25] The general conclusion is that the Ag substrate does not affect the dissociation mechanism but does influence subsequent dynamics. A trimodal (collisionless, intermediate, and thermal components) model was developed to interpret the observations.…”

Section: -Nm Tbn Photodissociation Processmentioning

confidence: 99%

Photodissociation at 193 nm of tert-Butyl Nitrite on Ag(111)

et al. 2004

Self Cite

View full text Add to dashboard Cite

The translational and internal state properties of nitric oxide, NO, ejected by 193-nm photodissociation of tert-butyl nitrite, (CH 3 ) 3 CONO, TBN, adsorbed on Ag(111) have been investigated using resonance-enhanced multiphoton ionization time-of-flight (REMPI-TOF) and quadrupole mass spectrometer time-of-flight (QMS-TOF). The results are described in terms of three components depending on the number of collisions along the exit trajectory and are compared to prior work using 248-and 351-nm photons. Although 193-nm photons have higher energy, the characteristic translational energy of the collisionless NO (0.55 eV) lies between that for 248 nm (0.89 eV) and 351 nm (0.39 eV). As for gas-phase photolysis at 193 nm, the NO is rotationally cold (J max ) 15.5), much lower than for both 248-(J max ) 53.5) and 351-nm (J max ) 31.5) photolysis. The NO vibrational distribution is dominated by V′′ ) 1, whereas V′′ ) 0 for 248 nm and V′′ ) 1 and 2 for 351 nm photodissociations, respectively. Angle-resolved REMPI-TOF and QMS-TOF studies give information about the orientation of adsorbed TBN. While TBN is more stable with the C-O-NdO plane perpendicular to surface and the internal O-N bond directed about 40°away from the surface normal, dosing less than a full monolayer at 80 K does not achieve this state fully. Annealing to 110 K is sufficient to realize this molecular orientation. For multilayer coverage dosed at 80 K, the data are consistent with considerable surface roughness compared to a surface annealed at 110 K. IntroductionSurface photochemistry has been of interest for many years. 1-3 Among the motivations are its many potential technological applications, e.g., photochemical lithography, deposition, and etching related to the fabrication of electronic and chemical sensor devices with submicron dimensions. There also continues to be scientific interest in fundamental questions concerning the mechanisms of energy transfer among the radiation field, and the various electronic and nuclear degrees of freedom of adsorbate-substrate systems.The spectroscopy and photodissociation dynamics of aliphatic nitrites (R-O-NdO) have been the subject of much interest. [4][5][6][7][8][9] Typically, gas phase and adsorbed nitrites dissociate upon photolysis and do so through cleavage of the internal O-N bond to from an alkoxide and nitric oxide. Like other nitrites, tertbutyl nitrite (TBN, (CH 3 ) 3 CONO) has three distinct optical absorption bands, the lowest energy band is found between 300 and 400 nm (n f π*, S 1 r S 0 ), and motion on S 1 is characterized as vibrational predissociation. The second band ranges from about 216 to 280 nm (π f π*, S 2 r S 0 ), and motion on S 2 is described as a very fast repulsive dissociation. The third band, rarely studied and related to this paper, ranges from 180 to 216 nm and also leads to dissociation of the internal O-N bond. State-resolved studies of NO reveal very different quantum state distributions depending on the photolysis wavelength. For gas-phase irradiation, photodissociation at 35...

show abstract

Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals

Richter‐Addo

2014

Progress in Inorganic Chemistry: Volume 59

View full text Add to dashboard Cite

State-resolved dynamics of NO produced by photodissociation of t-butyl nitrite on Ag(111)

Cited by 7 publications

References 32 publications

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

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

Photodissociation at 193 nm of tert-Butyl Nitrite on Ag(111)

Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals

Contact Info

Product

Resources

About