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Laser-induced UV photodissociation of 2-bromo-2-nitropropane: Dynamics of OH and Br formation
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10.1063/1.3532085
/content/aip/journal/jcp/134/4/10.1063/1.3532085
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/4/10.1063/1.3532085
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

LIF excitation spectrum of the (0,0) band of the A 2Σ+←X 2Π system of the nascent OH product from photodissociation of BNP (50 mTorr) at 193 nm.

Image of FIG. 2.
FIG. 2.

Boltzmann plots of rotational state population against energy of rotational states of OH(v″ = 0) generated in dissociation of BNP at 248 and 193 nm.

Image of FIG. 3.
FIG. 3.

Doppler profiles of P1(5) line of the A 2Σ+←X 2Π (0,0) system of the OH radical produced in dissociation of BNP at 248 and 193 nm. Points (square for 193 nm and circle for 248 nm) depict the experimental data, and the solid line is the Gaussian fit.

Image of FIG. 4.
FIG. 4.

Plots of Λ-doublet (left y axis, points marked as solid squares) and the spin-orbit state population ratio (right y axis, points marked as open circles) against rotational quantum number N″ for the nascent OH formed in laser-induced photodissociation of BNP at 248 nm (upper plot) and 193 nm (lower plot).

Image of FIG. 5.
FIG. 5.

The figure depicts the dispersed fluorescence spectrum at 150 ns delay with a broad peak at ∼540 nm, resulting from the photoexcitation of BNP at 193 nm.

Image of FIG. 6.
FIG. 6.

A typical observed fluorescence temporal profile (experimental points shown as open circles) at 540 nm after irradiation of BNP (175 mTorr) at 193 nm with a single-exponential fit (solid line) of its decay. The plot in the inset depicts the linear dependence of the fluorescence decay rates on varied pressures of BNP.

Image of FIG. 7.
FIG. 7.

REMPI spectral profiles of Br* and Br atoms produced in the 234 nm laser photolysis of BNP used for the determination of their ratio.

Image of FIG. 8.
FIG. 8.

REMPI-TOF profiles of Br(2P3/2) produced from the 234 nm photodissociation of BNP. The circles are the experimental data and the solid line is a forward convolution fit. Three panels, namely, upper, middle, and lower panels correspond to horizontal, magic angle, vertical, experimental geometries, respectively.

Image of FIG. 9.
FIG. 9.

REMPI-TOF profiles of Br*(2P1/2) produced from the 234 nm photodissociation of BNP. The circles are the experimental data and the solid line is a forward convolution fit. Three panels, namely, upper, middle, and lower panels correspond to horizontal, magic angle, vertical, experimental geometries, respectively.

Image of FIG. 10.
FIG. 10.

Photofragment speed distribution of Br(2P3/2) and Br*(2P1/2) determined for the 234 nm dissociation of BNP.

Image of FIG. 11.
FIG. 11.

The optimized structures of the ground electronic state of BNP and transition states of probable reactions producing OH. Details are given in the text. All structures are optimized at the B3LYP/6-311+G(d,p) level of theory. A few important bond lengths (in Å) are marked on structures. Dissociating bonds are depicted as dotted lines. Each TS structure is marked as TS-n, where n represents the reaction number.

Image of FIG. 12.
FIG. 12.

Relative potential energy diagrams for formation of OH from the ground electronic state of BNP. Details are given in the text. All energies (in kcal/mol) are at MP2/6-311+G(d,p) level of theory. Each TS is marked as TS-n, where n represents the reaction number. A number in parenthesis also stands for a reaction. The curves in bold, dashed–dotted, and dot represent mechanism for OH formation at 193 nm, 248 nm, and through nitrite form of BNP, respectively. The dashed curves represent a possible NO2 formation channel.

Image of FIG. 13.
FIG. 13.

Relative potential energy diagrams for formation of Br from the ground electronic state of BNP. All energies (in kcal/mol) are at MP2/6-311+G(d,p) level of theory. Each TS is marked as TS-n, where n represents the reaction number. A number in parenthesis also stands for a reaction.

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/content/aip/journal/jcp/134/4/10.1063/1.3532085
2011-01-28
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Laser-induced UV photodissociation of 2-bromo-2-nitropropane: Dynamics of OH and Br formation
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/4/10.1063/1.3532085
10.1063/1.3532085
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