Quadratic electro-optic effects (dc or low frequency Kerr effect) of bacteriorhodopsin dispersed in dried gelatin thin films are examined in the near resonance region at three wavelengths: 633, 647, and 676 nm. The films show relatively large quadratic electro-optic effects compared to other molecular dispersed systems. The purple membrane is fixed within the polymerized gelatin matrix, and we show that the electronic contribution to γ dominates over possible orientational contributions. At 676 nm. the quadratic electro-optic coefficient s1133( - ω;0,0,ω) is 6.7 × 10-20 m2/V2 and the third order nonlinear susceptibility X1133(3)(-ω;0,0,ω) is 7.0 × 10-13 cm4 statCoulomb-2, with both values obtained for a protein concentration of 6.9 × 1018 cm-3. The orientationally averaged second molecular hyperpolarizability 〈γ(-ω;0.0,ω)〉 determined from the quadratic electro-optic coefficients at 676 nm assuming an Onsager ellipsoidal local field factor is (10.8±5.1)×10-32 cm7 statCoulomb-2 [(1.34±0.63) × 10-56 F3 m4C-2]. The 〈γ(- ω;0,0,ω)〉 value increases roughly tenfold when the probe wavelength is decreased to 633 nm. The behavior of γ(-ω;0,0,ω), when fit to a two-state model, predicts that γ(- ω;0,0,ω) is strongly enhanced via type III processes. Thus, the magnitude of γ(-ω;0,0,ω) is dominated by a term (Δμ210×μ210)/(ω10-ω)3, where Δμ10 is the change in dipole moment, μ10 is the transition moment, and ω10 is the transition energy of the lowest-lying allowed 1Bw*+-like π,π* state. We calculate that Δμ10 is 12.8±1.2 D, in good agreement with previous Stark and two-photon experimental values. Time-dependent Hartree-Fock methods based on the MNDO Hamiltonian yield reasonable agreement with experiment, underestimating γ(-ω;0,0,ω) by factors of only 2-4, with the error increasing as the frequency approaches resonance.
Yamazaki, Mikio; Goodisman, Jerry; and Birge, Robert R., "Quadratic Electro-Optic Effects in Bacteriorhodopsin: Measurement of γ(-ω;0,0,ω) in Dried Gelatin Thin Films" (1998). Chemistry Faculty Scholarship. 15.
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