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Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution
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10.1063/1.4722084
/content/aip/journal/jcp/136/20/10.1063/1.4722084
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/20/10.1063/1.4722084

Figures

Image of Scheme 1.
Scheme 1.

The localized pictures of the electronic structures for S1(n, π*), T2(n, π*), T1(π, π*), and the S1/T1/T2 three-surface intersection from Ref. 8.

Image of Scheme 2.
Scheme 2.

Schematic excited state relaxation pathways for benzoic acid. Electronic characters of S1, S2, S3, T1, T2, the adiabatic transition energies (kcal/mol), transition states for various dissociation channels, dissociation products, and surface intersections of S2/S1, S2/T2, and S1/T1/T2 are all indicated. All the energy values are adapted from Ref. 8 or Ref. 12.

Image of FIG. 1.
FIG. 1.

(a) Steady-state FTIR spectrum of 32 mM benzoic acid in acetonitrile-d 3 solution. (b) Transient IR absorption spectra of 32 mM benzoic acid in acetonitrile-d 3 solution upon excitation of a femtosecond 267 nm pulse.

Image of FIG. 2.
FIG. 2.

Representative TR-IR kinetic traces for the T1 formation at 1586 cm−1 and ground state recovery at 1724 cm−1. Best fitting curves for the kinetics before 200 ps are shown in insets by solid lines.

Image of FIG. 3.
FIG. 3.

ns-TR-IR spectra of 32 mM benzoic acid in acetonitrile-d 3 solution (without deaeration by N2) following the 267 nm Nd:YVO4 laser excitation. Insets: Kinetic traces for T1 decay at 1586 cm−1 and ground state recovery at 1724 cm−1, along with the fitting shown by solid lines.

Image of FIG. 4.
FIG. 4.

Step-scan TR-FTIR absorption spectra of 32 mM benzoic acid in acetonitrile-d 3 solution obtained following the 193 nm nanosecond laser excitation.

Image of FIG. 5.
FIG. 5.

Transient UV-Vis absorption spectra of benzoic acid in acetonitrile solution obtained following the 266 nm or 193 nm nanosecond laser excitation. The UV absorbance at two wavelengths is adjusted to be identical for comparing the triplet yields. The kinetics traces in N2 or air-saturated conditions are also shown.

Tables

Generic image for table
Table I.

IR frequency and IR intensity calculated at the B3LYP/6-31+G(d) and D95(d,p) level with the solvent effect simulated by the PCM model. IR extinction coefficients (ɛ) are also listed.

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/content/aip/journal/jcp/136/20/10.1063/1.4722084
2012-05-30
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Ultrafast formation of the benzoic acid triplet upon ultraviolet photolysis and its sequential photodissociation in solution
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/20/10.1063/1.4722084
10.1063/1.4722084
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