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Reference molecules for nonlinear optics: A joint experimental and theoretical investigation
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10.1063/1.3675848
/content/aip/journal/jcp/136/2/10.1063/1.3675848
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/2/10.1063/1.3675848

Figures

Image of FIG. 1.
FIG. 1.

Polarization scan of the HRS response for an ideal octupolar molecule (dotted line: green online), for a dipolar molecule (solid line: red online) and a 1-D molecule (with only one non-vanishing component β zzz) (dashed line: black online).

Image of FIG. 2.
FIG. 2.

Experimental (points) and fitted curve (black dotted line) of the harmonic light intensity as a function of the incident state of polarization Ψ of the CCl4 molecule. The solid line (blue online) and dotted line (green online) represent the incoherent (octupolar) and coherent (dipolar) contributions, respectively.

Image of FIG. 3.
FIG. 3.

Experimental (points) and fitted curves (dotted lines) of the harmonic light intensity as a function of the polarization angle Ψ within an elliptical modulation of the fundamental light (δ = π/2) for (a) CHCl3, (b) CCl3–CN, (c) CH3–CN, and (d) CH2Cl2 molecules. Anisotropy factors and errors deduced from the fits are also indicated.

Image of FIG. 4.
FIG. 4.

Evolution of (a) the depolarization ratio DR and (b) the octupolar and dipolar contributions to the β responses with respect to the nonlinear anisotropy parameter. The squares correspond to the measured values for the various compounds.

Image of FIG. 5.
FIG. 5.

Evolution of the symmetry of the scattering structure of the five compounds. From left to right, in order of decreasing DR: CH3–CN, CH2Cl2, CCl3–CN, CHCl3, and CCl4. The thin and thick arrows indicate the polarization due to chlorine atoms and cyano groups, respectively. Bonds with hydrogens are not represented.

Image of FIG. 6.
FIG. 6.

Evolution of (a) the static HRS hyperpolarizabilities and (b) depolarization ratios of the various compounds as a function of the number of valence AOs in the aug-cc-pVXZ basis sets (X = 2 to 6).

Image of FIG. 7.
FIG. 7.

Evolution of (a) the static HRS hyperpolarizabilities and (b) depolarization ratios of the various compounds (calculated accounting for solvent effects) as a function of the number of valence AOs in the aug-cc-pVXZ basis sets (X = 2 to 6).

Image of FIG. 8.
FIG. 8.

Evolution of the depolarization ratio DR (left) and of the octupolar and dipolar contributions (right) with respect to the nonlinear anisotropy parameter. Black squares correspond to measured values, and red circles correspond to dynamic CCSD(T) results obtained using the multiplicative scheme.

Image of FIG. 9.
FIG. 9.

Two-dimensional (left) and polar (right) representations of the evolution of the intensity of the harmonic light as a function of the polarization angle Ψ of the incident beam. Red circles correspond to measured values, while lines correspond to frequency-dependent values obtained using Eq. (20) in combination with various levels of calculations and the d-aug-cc-pVTZ basis set. Solvent effects were taken into account via the IEF-PCM scheme.

Tables

Generic image for table
Table I.

Dielectric constants in the static limit (ɛ 0) and at infinite frequency (ɛ ), refractive indices at ω and 2ω, Lorentz-Lorenz local field factors, and molarities C for the various liquids used in the HRS experiments.

Generic image for table
Table II.

β HRS and β J values (in atomic unitsa, using convention T) as well as their ratios deduced from HRS measurements. For CCl4, only the incoherent part is considered (see text for more details).

Generic image for table
Table III.

Numbers of contracted Gaussian functions in the various basis sets. When different, the numbers of basis functions effectively used in the calculations are given in parentheses.

Generic image for table
Table IV.

Static (λ = ∞) and dynamic (λ = 1064 nm) HRS hyperpolarizabilities (in atomic units, using T convention) and depolarization ratios calculated at the HF level in gas phase.

Generic image for table
Table V.

Static (λ = ∞) and dynamic (λ = 1064 nm) HRS hyperpolarizabilities (in atomic units, using T convention) and depolarization ratios calculated at the TDHF level. Solvent effects are included via the IEF-PCM scheme.

Generic image for table
Table VI.

Static (λ = ∞) HRS hyperpolarizabilities (in atomic units, using T convention) and depolarization ratios calculated using various ab initio levels in combination with the (d)-aug-cc-pVTZ basis set, with and without including solvent effects.

Generic image for table
Table VII.

β Liq/β Gas ratios, as calculated at the HF and CCSD(T) levels of approximation using the d-aug-cc-pVTZ basis set in comparison to HRS experiments. Dynamic (λ = 1064 nm) CCSD(T) results were obtained using the multiplicative scheme (Eq. (20)).

Generic image for table
Table VIII.

Dynamic (λ = 1064 nm) β HRS and β J values (in atomic units, using convention T), ρ = |β J = 3|/|β J = 1| ratios as well as depolarization ratios calculated at the HF and CCSD(T) levels of approximation using the d-aug-cc-pVTZ basis set. Solvent effects were accounted for using the IEF-PCM scheme. Dynamic CCSD(T) β HRS and DR results were obtained using the multiplicative scheme (Eq. (20)) while the corresponding |β J = 1| and |β J = 3| were evaluated using Eqs. (13) and (14).

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/content/aip/journal/jcp/136/2/10.1063/1.3675848
2012-01-13
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Reference molecules for nonlinear optics: A joint experimental and theoretical investigation
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/2/10.1063/1.3675848
10.1063/1.3675848
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