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Influence of anion on the quadratic nonlinearity and depolarization ratios of scattered second harmonic light from cation-π complexes
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10.1063/1.4716020
/content/aip/journal/jcp/136/19/10.1063/1.4716020
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/19/10.1063/1.4716020

Figures

Image of FIG. 1.
FIG. 1.

Schematic representation of the polarization resolved HRS measurement. The incident beam is propagating along the Z axis and is polarized along the X axis. The SH-scattered light is measured along the Y axis with the polarization along the X and the Z axes.

Image of FIG. 2.
FIG. 2.

Tropylium cation and π donors chosen for this study.

Image of FIG. 3.
FIG. 3.

Normalized second harmonic intensity, I/Iω 2 as a function of concentration of the TRO-MES complex.

Image of FIG. 4.
FIG. 4.

The centre of mass of the cationic complex consisting of the substituted benzene (R is either CH3 or H) donor and the tropylium acceptor pair at the origin of the reference frame. The centre of mass of the BF4 counterion is placed at a distance of 6.5 Å along the x axis. The angle θ describes the rotation of BF4 about the z axis whereas ϕ describes the same about the y axis.

Image of FIG. 5.
FIG. 5.

Trigonal arrangement in solution with 3 C-BF4 moieties that is used for calculating the NLO coefficients of the cation-π complex. C stands for the complex between tropylium cation and the substituted methyl benzene.

Tables

Generic image for table
Table I.

Experimental β HRS values, wavelength of maximum absorption (λ max), and molar extinction coefficient (ɛ) at λ max for the cation-π complexes in acetonitrile.a

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Table II.

Measured linear and circular depolarization ratios for the cation-π complexes in acetonitrile.

Generic image for table
Table III.

Selected structural parameters of the CT complexes in their ground state optimized geometries. The distances are between an atom in the donor molecule and an atom in the acceptor molecule in the MP2/6-31g* (CP) optimized geometry. The last column gives the angle between the molecular planes of the donor and the acceptor moieties.

Generic image for table
Table IV.

Vertical singlet excitation energies (in some cases lowest two energies) of all the CT complexes and their oscillator strengths (in parenthesis) are shown. Calculated tumbling averaged first hyperpolarizability ||β|| and the linear and circular depolarization ratios are also given in the table.

Generic image for table
Table V.

Calculated linear and nonlinear optical properties of the three cation-π-BF4 complexes, arranged in a C3 symmetric fashion (Fig. 5). The oscillator strengths corresponding to excitation energies are given in parentheses next to the gaps. All the calculations are performed in acetonitrile using the SCRF model within a correction vector (CV) approach. D and D are the linear and circular depolarization ratios, respectively. Angles θ and ϕ are defined in Fig. 4.

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/content/aip/journal/jcp/136/19/10.1063/1.4716020
2012-05-17
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Influence of anion on the quadratic nonlinearity and depolarization ratios of scattered second harmonic light from cation-π complexes
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/19/10.1063/1.4716020
10.1063/1.4716020
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