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Vibronic coupling in asymmetric bichromophores: Theory and application to diphenylmethane
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10.1063/1.4747336
/content/aip/journal/jcp/137/8/10.1063/1.4747336
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/8/10.1063/1.4747336

Figures

Image of FIG. 1.
FIG. 1.

Potential energy surfaces for the ground (black) and excited (red) electronic state along vibrational mode Q. E e is the vertical excitation energy and is the displacement between the two minima.

Image of FIG. 2.
FIG. 2.

Model spectra of one intra-monomer vibrational mode in strong coupling regime with different frequencies on either monomer. ω A = 150 cm−1, ω B = 150 + δ cm−1, b A = b B = 1.0, V AB = 400 cm−1. The first row is absorption, the second row is S 1 emission, and the third row is S 2 emission. δ = 0 in (a)–(c); δ = 30 cm−1 in (d)–(f); δ = 75 cm−1 in (g)–(i).

Image of FIG. 3.
FIG. 3.

Model spectra of one intra-monomer vibrational mode in strong coupling regime with different displacements on either monomer. ω A = ω B = 150 cm−1, b A = 1.0, b B = 1.0 + δ, V AB = 400 cm−1. The first row is absorption, the second row is S 1 emission, and the third row is S 2 emission. δ = 0 in (a)–(c); δ = 0.3 in (d)–(f); δ = 0.6 in (g)–(i).

Image of FIG. 4.
FIG. 4.

Model spectra of one intra-monomer vibrational mode in weak coupling regime with different displacements on either monomer. ω A = ω B = 300 cm−1, b A = 0.6, b B = 0.6 − δ, V AB = 50 cm−1. The first row is absorption, the second row is S 1 emission, and the third row is S 2 emission. δ = 0 in (a)–(c); δ = 0.2 in (d)–(f); δ = 0.4 in (g)–(i).

Image of FIG. 5.
FIG. 5.

Model spectra of one inter-monomer vibrational mode with different frequencies in the ground and first and second excited states of the dimer. V AB = 300 cm−1, b = b + = 0.8 in all spectra. ω g · s = ω = ω+ = 100 cm−1 in (a)–(c); ω g · s = 100 cm−1, ω = 150 cm−1, ω+ = 100 cm−1 in (d)–(f); ω g · s = 100 cm−1, ω = 150 cm−1, ω+ = 80 cm−1 in (g)–(i). The first row is absorption, the second row is S 1 (S ) emission, and the third row is S 2 (S +) emission. Changing the frequency of one state does not change the spacing between frequency levels for the other state.

Image of FIG. 6.
FIG. 6.

Model spectra of one inter-monomer vibrational mode with different displacement parameters for the S 1 and S 2 states of the dimer. V AB = 300 cm−1, ω g · s = ω = ω+ = 100 cm−1 in all spectra. b = b + = 0.8 in (a)–(c); b = 0.4, b + = 0.8 in (d)–(f); b = 0.0, b + = 0.8 in (g)–(i). The first row is absorption, the second row is S 1 (S ) emission, and the third row is S 2 (S +) emission. Changing the displacement for one state allows to suppress the Frank-Condon progression on this state while keeping it on the other.

Image of FIG. 7.
FIG. 7.

Potential energy surfaces of the symmetric torsion T mode in (a) the second excited state, (b) the first excited state, and (c) the ground state. The abscissa is the displacement from the optimized S 1 geometry. Energy scales in frames (a)–(c) are different because near the S 1 minimum, the PES of the S 1 state is dominated by second order effects while PESs of the other two states are dominated by first order effects.

Image of FIG. 8.
FIG. 8.

DPM spectra produced from parameters in Tables I and III with an electronic coupling constant of 155.8 cm−1. Comparison of the calculated (red) and experimental (black) absorption spectra is shown in (a). Breakdown of the calculated spectrum by the electronic state, with the red trace representing the S 1 (anti-symmetric) state and the blue trace representing the S 2 (symmetric) state in (b). (c) and (d) Comparisons of the calculated (red) and experimental (black) emission spectra from the S 1 and S 2 origins, respectively.

Image of FIG. 9.
FIG. 9.

S 2 “clump” emission spectra. The calculated spectrum (in red) is produced by adding S 2 emission spectrum as in Fig. 8(d) with emissions from energetically close S 1 vibrational states. Experiential spectrum is in black.

Tables

Generic image for table
Table I.

Intra-monomer vibrational parameters for diphenylmethane as found from B3LYP/cc-pVTZ calculations on toluene.

Generic image for table
Table II.

Inter-monomer vibrational parameters as found from B3LYP/cc-pVTZ calculations on S 0, S 1, and S 2 states of diphenylmethane.

Generic image for table
Table III.

Adjusted (fitted to experimental spectra) inter-monomer vibrational parameters. Calculated values were kept where appropriate.

Generic image for table
Table IV.

Vertical S 1S 2 splittings computed at the ground state optimized geometry.a

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/content/aip/journal/jcp/137/8/10.1063/1.4747336
2012-08-30
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Vibronic coupling in asymmetric bichromophores: Theory and application to diphenylmethane
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/8/10.1063/1.4747336
10.1063/1.4747336
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