By William Barford
Conjugated polymers have very important technological functions, together with sun cells and light-weight emitting monitors. also they are lively parts in lots of organic methods. in recent times, there were major advances in our realizing of those structures, because of either better experimental measurements and the advance of complex computational options. the purpose of this publication is to explain and clarify the digital and optical houses of conjugated polymers. It specializes in the nature and lively ordering of the digital states and relates those houses to experimental observations in actual structures.
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Extra resources for Electronic and Optical Properties of Conjugated Polymers
Sample text
9) with k replaced by β. Thus, the energy of the molecular-orbital state, |β , is, β = −2t cos(βa). 16) This dispersion is shown in Fig. 2. The molecular-orbital functions, ψβ (r), are constructed in exact analogy to the Bloch functions of the last section. Thus, we have, N ψβ (r) ≡ r|β = 2 φn (r) sin(βna). 18) where the eigenvalue, i(β), is +1 for odd quantum number j and −1 for even quantum number j. 4 Dimerized chains The unit cell for a dimerized chain is shown in Fig. 3. There are two sites per unit cell, and two different hybridization integrals, td = t(1+δ) and ts = t(1−δ), representing the ‘double’ (short) and ‘single’ (long) bonds, respectively.
1 Wannier States By Fourier transforming the Bloch operators, ckσ v † c obtain Wannier operators, c σ , which create electrons in Wannier states localized on the th repeat unit: v † c cσ = 1 Nu v † c ckσ exp(i2k a). 25) k To a rather good approximation,13 the valence and conduction band Wannier states are equivalent to the bonding and antibonding states, respectively, that is, v 1 † c cσ ≈ √ c†2 −1 ± c†2 . 26) 2 12 For 1/2 a general td and ts the energy spectrum is k = ± t2d + t2s + 2td ts cos(2ka) .
This is also the energy of the lowest particle-hole excitation. Now, in a noninteracting model the singlet and triplet excitations are degenerate, so the band gap is equivalent to both the charge and spin gaps. 40) where E0 (M ) is the ground state energy for M electrons. This is obviously equivalent to the band gap, and it is the energy of an uncorrelated particle-hole pair. For short linear chains the charge gap scales linearly with 1/N , but for long chains it scales as 1/N 2 , approaching 4δt in the infinite chain limit.
