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Experimental and theoretical study of the photodissociation reaction of thiophenol at : Intramolecular orbital alignment of the phenylthiyl radical
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10.1063/1.2424939
/content/aip/journal/jcp/126/3/10.1063/1.2424939
http://aip.metastore.ingenta.com/content/aip/journal/jcp/126/3/10.1063/1.2424939

Figures

Image of FIG. 1.
FIG. 1.

(a) 2D projection of the 3D spatial distribution of D ion, (b) the center slice of the reconstructed 3D distribution, and (c) experimental setup used. The vertical arrow in (a) and (c) indicates the polarization of the pump laser. M: mirror, FL: focusing lens, PO: polarizing optics, IO: ion optics, and PSD: position sensitive detector.

Image of FIG. 2.
FIG. 2.

(Color online) The total translational energy distribution and associated anisotropy parameter. Open circles are showing the total translation energy distribution, while the (red) dotted and (blue) solid lines represent the translational energy distribution for the and channels, respectively. The averaged anisotropy parameter as a function of the total translation energy is shown as the filled rectangle and used for the deconvolution of the translational energy distribution (see the text).

Image of FIG. 3.
FIG. 3.

(Color online) Natural orbitals for the singly occupied (SO) molecular orbital (MO), highest doubly occupied MO (HOMO), and second HOMO (HOMO-1) of the (a) ground state and the (b) first electronically excited state of thiophenol radical.

Image of FIG. 4.
FIG. 4.

(Color online) Schematic diagram showing that the photodissociation of gives rise to intermolecular orbital alignment.

Image of FIG. 5.
FIG. 5.

(Color online) Absorption spectrum of thiophenol taken in -hexanes. The pump energy of used in this work is indicated as an arrow.

Image of FIG. 6.
FIG. 6.

Calculated potential energy curves of thiophenol as a function of S–H coordinate dissociating to the two lowest states of radical. The energy profile is obtained at the MRCI level. HOMO/SOMO is also shown.

Image of FIG. 7.
FIG. 7.

(Color online) Diabatic (solid line) and spin-orbit coupled (dotted line) potential energy curves of thiophenol as a function of S–H coordinate dissociating to the two lowest states of phenylthiyl radical.

Image of FIG. 8.
FIG. 8.

(Color online) Potential energy curves of thiophenol as a function of S–H distance obtained at the MRCI level. Solid lines indicate singlet states and dotted lines the triplet states.

Image of FIG. 9.
FIG. 9.

(Color online) (a) 2D projection of the 3D spatial distribution of the H fragment, (b) the center slice of the reconstructed 3D distribution, and (c) the total transnational energy distribution from the photodissociation at . The contribution only from the S–H bond dissociation is obtained by the deconvolution of the two distinct peaks out of the isotropic broad background feature. Open circles are showing the total translation energy distribution, while the (red) dotted and (blue) solid lines represent the isotropic background and anisotropic H ion signals, respectively (see the text).

Tables

Generic image for table
Table I.

The energy disposal into the and states of the phenylthiyl radical in the photodissociation of at . (All values are in kcal/mol.)

Generic image for table
Table II.

The S–H(D) bond dissociation energy of thiophenol in kcal/mol. (All previous reported and theoretical values are those of the S–H bond dissociation energy.)

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/content/aip/journal/jcp/126/3/10.1063/1.2424939
2007-01-17
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Experimental and theoretical study of the photodissociation reaction of thiophenol at 243nm: Intramolecular orbital alignment of the phenylthiyl radical
http://aip.metastore.ingenta.com/content/aip/journal/jcp/126/3/10.1063/1.2424939
10.1063/1.2424939
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