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A multireference perturbation study of the NN stretching frequency of trans-azobenzene in nπ* excitation and an implication for the photoisomerization mechanism
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10.1063/1.4790611
/content/aip/journal/jcp/138/6/10.1063/1.4790611
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/6/10.1063/1.4790611

Figures

Image of FIG. 1.
FIG. 1.

A scheme of rotation and inversion mechanism for cis-trans isomerization of azobenzene.

Image of FIG. 2.
FIG. 2.

Natural orbitals corresponding to (a) the lone pair orbital of nitrogen and (b) the NN anti-bonding π* orbital of trans-azobenzene related to nπ* excitation determined by the SA-CASSCF(6,4) calculation at (S0)min.

Image of FIG. 3.
FIG. 3.

A scheme of the mixing between the NN stretching mode and the CN symmetric stretching mode due to nπ* excitation.

Image of FIG. 4.
FIG. 4.

Variations of (a) S0 and S1 energies, (b) important geometrical parameters, and (c) the NN stretching frequency along the rotation pathway.

Image of FIG. 5.
FIG. 5.

A set of natural orbitals in the active space of SA-CASSCF(6,4) wavefunction at (a) d CNNC = 180° ((S1-C2h)min), (b) d CNNC = 140°, and (c) d CNNC = 100°, along the rotation pathway. The corresponding orbital set at a NNC1 = 180° on the inversion pathway is also given in (d).

Image of FIG. 6.
FIG. 6.

Variations of (a) S0 and S1 energies, (b) important geometrical parameters, and (c) the NN stretching frequency along the inversion pathway.

Tables

Generic image for table
Table I.

Geometrical parameters (bond length r in Å; bond angle a in degrees) and the harmonic frequency corresponding to the N-N stretching mode (ν NN in cm−1) in the ground state.

Generic image for table
Table II.

Geometrical parameters (bond length r in Å; bond angle a in degrees) and the NN stretching harmonic frequency (ν NN in cm−1) for the C2h-optimized structure in the S1(nπ*) state, as well as nπ* vertical and adiabatic excitation energies (ΔE adi and ΔE ver in eV) within C2h point group.

Generic image for table
Table III.

Geometrical parameters (bond length r in Å; bond angle a in degrees) of trans-diazene and harmonic frequencies for the NN stretching mode and the HNNH torsional mode (ν NN, ν HNNH in cm−1) for C2h-optimized structure in the S0 and S1(nπ*) states, as well as nπ* vertical and adiabatic excitation energies (ΔE ver and ΔE adi in eV) within C2h point group at the CASPT2(12,10)/DZP level.

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/content/aip/journal/jcp/138/6/10.1063/1.4790611
2013-02-13
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A multireference perturbation study of the NN stretching frequency of trans-azobenzene in nπ* excitation and an implication for the photoisomerization mechanism
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/6/10.1063/1.4790611
10.1063/1.4790611
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