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Infrared identification of the σ-complex of Cl-C6H6 in the reaction of chlorine atom and benzene in solid para-hydrogen
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10.1063/1.4790860
/content/aip/journal/jcp/138/7/10.1063/1.4790860
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/7/10.1063/1.4790860

Figures

Image of FIG. 1.
FIG. 1.

Geometries of (a) η6 π-complex, (b) η2 π-complex, (c) σ-complex, and (d) η1 π-complex predicted with the MPW1PW91/6-311++G(2d,2p) method. Bond distances are given in Å, and angles in degrees. For (c) and (d), a graphical representation of the bonding mechanism is also shown in a form of the bonding orbital.

Image of FIG. 2.
FIG. 2.

(a) IR absorption spectra of a Cl2/C6H6/p-H2 (1/1/1500) matrix sample after deposition at 3.2 K for 5 h. (b) Difference spectra after irradiation of the matrix with a LED at 365 nm for 1 h. (c) After annealing the sample at 5 K for 2 min. (d) After secondary photolysis at 3.2 K in the range 455–700 nm from a Hg lamp for 1 h. Lines of the C6H6-Cl2 complex are indicated with asterisks (*). New lines attributable to Cl-C6H6 are indicated with arrows.

Image of FIG. 3.
FIG. 3.

(a) Difference IR absorption spectra of a Cl2/C6H6/p-H2 (1/1/1500) matrix sample after secondary photolysis in the range 455–700 nm from a Hg lamp at 3.2 K for 1 h; the matrix was deposited at 3.2 K for 5 h, followed by irradiation with a LED at 365 nm for 1 h and annealing the sample at 5 K for 2 min. Lines of C6H6 are removed for clarity. IR spectra of the σ-complex (b) and the η1 π-complex (c) of Cl-C6H6 simulated according to the anharmonic vibrational frequencies and IR intensities predicted with the MPW1PW91/6-311++G(2d,2p) method. New lines attributable to Cl-C6H6 are indicated with arrows.

Image of FIG. 4.
FIG. 4.

(a) Inverted difference IR absorption spectra of a Cl2/C6D6/p-H2 (1/1/2000) matrix sample after secondary photolysis in the range 455–700 nm from a Hg lamp at 3.2 K for 1 h; the matrix was deposited at 3.2 K for 5 h, followed by irradiation with a LED at 365 nm for 1 h and annealing the sample at 5 K for 2 min. (b) Lines of C6H6 are removed for clarity. IR spectra of the σ-complex. (c) The η1 π-complex of Cl-C6D6 simulated according to the anharmonic vibrational frequencies and IR intensities predicted with the MPW1PW91/6-311++G(2d,2p) method. New lines attributable to Cl-C6H6 are indicated with arrows.

Tables

Generic image for table
Table I.

Comparison of experimentally observed line positions (cm−1) and intensities with the computed MPW1PW91/6-311++G(2d,2p) anharmonic vibrational wavenumbers (cm−1) and IR intensities of the σ- and π-complexes of Cl-C6H6.

Generic image for table
Table II.

Comparison of experimentally observed line positions (cm−1) and intensities with the computed MPW1PW91/6-311++g(2d,2p) anharmonic vibrational wavenumbers (cm−1) and IR intensities of the σ- and π-complexes of Cl-C6D6.

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/content/aip/journal/jcp/138/7/10.1063/1.4790860
2013-02-19
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Infrared identification of the σ-complex of Cl-C6H6 in the reaction of chlorine atom and benzene in solid para-hydrogen
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/7/10.1063/1.4790860
10.1063/1.4790860
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