From Monomers to Clusters. Photodissociation of tert-Butyl Nitrite (CH3)3CONO and Homogeneous [(CH3)3CONO]n Clusters

Kades, E.; Roesslein, M.; Huber, J. Robert

doi:10.1021/j100102a021

Cited by 30 publications

(33 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…into the k = 0 progression member. 15 The product yield spectra reported in this paper show quite a substantial yield of NO in v = 0. Also, for excitation into k = 1 and k = 2 the yield of NO(v = k) is greater or comparable to the yield of NO(v = k À 1).…”

mentioning

confidence: 56%

“…This has been concluded from the observation of bimodal distributions of the rotational population in the NO photodissociation products. 14,15 However, in a later publication such bimodal rotational distributions have been linked to a second decay channel employing a linear O-NO transition state on the excited state potential energy surface.…”

Section: Separation Of Clusters From Monomersmentioning

confidence: 99%

“…By application of these techniques a wealth of information has been gathered on the photodissociation dynamics of alkyl nitrites, in particular for methyl nitrite CH 3 ONO 1-8 and t-BuONO. [8][9][10][11][12][13][14][15][16][17][18][19] Reviews of this earlier work can be found in ref. 20 and 21. In spite of this there are two good reasons for further studies on this class of compounds.…”

Section: Introductionmentioning

confidence: 99%

“…193 nm) only NO fragments in the electronic ground state 2 P have been observed, with similar populations in the two spin-orbit substates. Rotational state distributions were always non-statistical, usually well described by Gaussians that peak at J E 35 9,15 for photolysis via the S 1 state, and at J E 55 for photolysis via the S 2 state. 13 Bimodal distributions were reported in several studies and assigned to either clusters 14,15 or a second dissociation channel.…”

Section: Introductionmentioning

confidence: 99%

“…19 Experiments performed with MeONO have led to the conclusion that the preferred vibrational quantum number v in the NO fragment produced by dissociation following excitation to the progression member k is one less than the excited quantum number. 15 Such a propensity for v = k À1 would indicate a vibrational predissociation mechanism. Similar conclusions have been drawn from lifetimes for the S 1 states of MeONO (125 AE 50 fs) and t-BuONO (130 AE 20 fs).…”

mentioning

confidence: 99%

See 4 more Smart Citations

Photodissociation dynamics of tert-butylnitrite following excitation to the S1 and S2 states. A study by velocity-map ion-imaging and 3D-REMPI spectroscopy

Wenge

Schmaunz

Kensy

et al. 2012

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Excitation of tert-butylnitrite into the first and second UV absorption bands leads to efficient dissociation into the fragment radicals NO and tert-butoxy in their electronic ground states 2 P and 2 E, respectively. Velocity distributions and angular anisotropies for the NO fragment in several hundred rotational and vibrational quantum states were obtained by velocity-map imaging and the recently developed 3D-REMPI method. Excitation into the well resolved vibronic progression bands (k = 0, 1, 2) of the NO stretch mode in the S 1 ' S 0 transition produces NO fragments mostly in the vibrational state with v = k, with smaller fractions in v = k À 1 and v = k À 2. It is concluded that dissociation occurs on the purely repulsive PES of S 1 without barrier. All velocity distributions from photolysis via the S 1 (np*) state are monomodal and show high negative anisotropy (b E À1). The rotational distributions peak near j = 30.5 irrespective of the vibronic state S 1 (k) excited and the vibrational state v of the NO fragment. On average 46% of the excess energy is converted to kinetic energy, 23% and 31% remain as internal energy in the NO fragment and the t-BuO radical, respectively. Photolysis via excitation into the S 2 ' S 0 transition at 227 nm yields NO fragments with about equal populations in v = 0 and v = 1. The rotational distributions have a single maximum near j = 59.5. The velocity distributions are monomodal with positive anisotropy b E 0.8. The average fractions of the excess energy distributed into translation, internal energy of NO, and internal energy of t-BuO are 39%, 23%, and 38%, respectively. In all cases B8500 cm À1 of energy remain in the internal degrees of freedom of the t-BuO fragment. This is mostly assigned to rotational energy. An ab initio calculation of the dynamic reaction path shows that not only the NO fragment but also the t-BuO fragment gain large angular momentum during dissociation on the purely repulsive potential energy surface of S 2 .

show abstract

mentioning

confidence: 56%

Section: Separation Of Clusters From Monomersmentioning

confidence: 99%