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Organic Electronic Devices Week 2: Electronic Structure Lecture 2.3: Application of the Schrödinger Equation

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Organic Electronic Devices Week 2: Electronic Structure Lecture 2.3: Application of the Schrödinger Equation Organic Electronic Devices Week 2: Electronic Structure Lecture 2.3: Application of the Schrödinger Equation Bryan W. Boudouris Chemical Engineering Purdue University 1 Lecture Overview and Learning Objectives • Concepts to be Covered in this Lecture Segment • Implementation of the Time-independent Schrödinger Equation in Order to Solve for Transition Energies • Derivation of the Three-Dimensional Time-independent Schrödinger Equation • Extension of the Three-Dimensional Time-independent Schrödinger Equation to Wavevector Surfaces • Learning Objectives By the Conclusion of this Presentation, You Should be Able to: 1. Solve for the transition energy values in simple organic molecule systems using the Time-independent Schrödinger Equation. 2. Derive the three-dimensional, time-independent Schrödinger equation using the separation of variables method. 3. Convert between real space and wavevector space. The Energy of the Electron is a Function of the Quantum Number Recall from the Previous Lecture That the Following Holds for an Free Electron Contained within a Well with Walls at Infinite Potential Energy nπ ψ = n (x) sin (x) L n2h2 E = n 8mL2 Note That as the Quantum Number (n) increases, the energy increases. Furthermore, the “length of the box” plays an important role in the calculated energy. Estimating Energetic Transitions in Molecules Using This Model Example: The HOMO to LUMO Transition Energy in 1,3-Butadiene 1,3-Butadiene Assume that the Molecule is Linear 4 Carbons with sp2 Hybridized Orbitals (i.e., Do Not Consider Bond Angles) 2 C=C Double Bonds (0.135 nm): 0.270 nm 1 C-C Single Bond (0.154 nm): 0.154 nm 2 Carbon Radii (0.077nm): 0.154 nm 4 Frontier pz Orbitals for π-Bonding Summing These Values Gives L * π4 L = 0.578 nm * π3 n2h2 π E = or 2 n 8mL2 pz pz pz pz ( j 2 − i2 )h2 ∆ = Ei→ j 2 8me L π1 Further Reading: Physical Chemistry: A Molecular Approach by Donald A. McQuarrie and John D. Simon Estimating the HOMO to LUMO Transition Energy in 1,3-Butadiene Example: The HOMO to LUMO Transition Energy in 1,3-Butadiene (32 − 22 )h2 ∆ = ∆ = EHOMO→LUMO E2→3 2 8me L (32 − 22 )h2 (9 − 4)×(6.626×10−34 J ⋅ s)2 ∆ = = E2→3 2 −31 −9 2 8me L 8×(9.109×10 kg)×(0.578×10 m) −19 ∆E2→3 = 9.02×10 J = 5.63eV Measured Transition Energy: 5.71 eV; Difference: 1.4% For Simple Systems, Such as the One Used Here, This Simple Model Works Further Reading: Physical Chemistry: A Molecular Approach by Donald A. McQuarrie and John D. Simon Extension of the Schrödinger Equation to 3 Dimensions Recall the Time-Independent Schrödinger Equation in 1 Dimension 2 ∂ 2ψ (x) − +V (x)ψ (x) = Eψ (x) 2m ∂x2 If The Case of the Free Electron (V = 0), Then the Equation Can be Transformed 2 2 ∂2ψ (x, y, z) ∂2ψ (x, y, z) ∂ 2ψ (x, y, z) − ∇2ψ = − + + = ψ (x, y, z) 2 2 2 E (x) 2m 2m ∂x ∂y ∂z The Dimensions of the Box Are Now: 0 ≤ x ≤ Lx ; 0 ≤ y ≤ Ly ; 0 ≤ z ≤ Lz And the Boundary Conditions for the Box Are: ψ (x = 0, y, z) =ψ (x = Lx , y, z) = 0 for all y and z ψ (x, y = 0, z) =ψ (x, y = Ly , z) = 0 for all x and z ψ (x, y, z = 0) =ψ (x, y, z = Lz ) = 0 for all x and y Separation of Variables Can Be Used to Solve for the Energy We Can Rewrite the 3-dimensional Wavefunction As: ψ (x, y, z) = X (x)Y (y) Z(z) This Form Can Now Be Substituted Into the Equation on the Previous Slide 2 ∂ 2ψ (x, y, z) ∂ 2ψ (x, y, z) ∂ 2ψ (x, y, z) − + + = ψ 2 2 2 E (x, y, z) 2m ∂x ∂y ∂z 2 ∂ 2 X (x)Y (y)Z(z) ∂ 2 X (x)Y (y)Z(z) ∂ 2 X (x)Y (y)Z(z) = − + + = ψ 2 2 2 E (x, y, z) 2m ∂x ∂y ∂z 2 d 2 X (x) d 2Y (y) d 2Z(z) = − + + = ψ Y (y)Z(z) 2 X (x)Z(z) 2 X (x)Y (y) 2 E (x, y, z) 2m dx dy dz 2 d 2 X (x) d 2Y (y) d 2Z(z) = − + + = Y (y)Z(z) 2 X (x)Z(z) 2 X (x)Y (y) 2 E X (x)Y (y) Z(z) 2m dx dy dz Dividing Each Side of the Equation by the Wavefunction Yields: 2 1 d 2 X (x) 1 d 2Y (y) 1 d 2Z(z) = − + + E 2 2 2 2m X (x) dx Y (y) dy Z(z) dz Separation of Variables Can Be Used to Solve for the Energy (Part II) Each Term on the Right Side of the Equation is a Function of a Single Variable E = Ex + Ey + Ez where : 2 1 d 2 X (x) 2 1 d 2Y (y) 2 1 d 2Z(z) E = − ; E = − ; E = − x 2m X (x) dx2 y 2m Y (y) dy 2 z 2m Z(z) dz 2 The Transformation of Variables Yields The Following Boundary Conditions: X (x = 0) = X (x = Lx ) = 0 Y (y = 0) = Y (y = Ly ) = 0 Z(z = 0) = Z(z = Lz ) = 0 Using the Same Mathematical Logic As for the 1-Dimensional Case Yields: π nx π x ny y nz π z X (x) = Ax sin ; Y (y) = Ay sin ; Z(z) = Az sin Lx Ly Lz Separation of Variables Can Be Used to Solve for the Energy (Part III) If One Normalizes the Probability of Finding the Electron Over Space to 1 Then: 1/ 2 8 = Ax Ay Az Lx Ly Lz Combining These Equations with the Original Wavefunction Definition Yields: ψ (x, y, z) = X (x)Y (y) Z(z) 1/ 2 8 n π x ny π y n π z ψ (x, y, z) = sin x sin sin z nxnynz Lx Ly Lz Lx Ly Lz Inserting This Form of the Wavefunction Into the Energy Expression Yields: 2 2 2 2 h n ny n E = x + + z This Is Very Similar to the nxnynz 2 2 2 1-Dimensional Solution 8m Lx Ly Lz The Presence of Symmetry Leads to Energy Level Degeneracy Even for an Equal-Sided Box, Added Dimensions Yield Added Complexity 2 2 2 2 h n ny n E = x + + z ; if L = L = L = L nxnynz 2 2 2 x y z 8m Lx Ly Lz [n2 + n2 + n2 ] h2 x y z E = [n2 + n2 + n2 ] Degeneracy nxnynz 2 x y z 8mL (3,2,1);(3,1,2);(2,3,1) 14 6 (1,3,2);(1,2,3);(2,1,3) For a Given Length of a Side 12 (2,2,2) 1 and a Given Mass, Different Combinations of the 11 (3,1,1);(1,3,1);(1,1,3) 3 Quantum Numbers Can Lead 9 (2,2,1);(2,1,2);(1,2,2) 3 to the Same (Degenerate) Energy Values 6 (2,1,1);(1,2,1);(1,1,2) 3 In Quantum Mechanics, Degeneracy is Considered an Underlying Sign of Symmetry 3 (1,1,1) 1 in the System The Energy Equation Can Be Expanded to Surfaces Recall from Last Lecture the Definition of the Wavevector (k) ni π ki = Li Therefore, the Energy Equation Can be Written As: 2 2 2 2 h k k y k E = x + + z nxnynz 2 2 2 8m π π π 2 2 2 2 E = [k + k + k ] nxnynz 2m x y z This 3-Dimensional Description Can Be Converted to a Sphere with a Surface at a Distance (kF) from the (0,0,0) Point in Space. This is Known as the Fermi Surface. Summary and Preview of the Next Lecture 9h2 Applying the concepts of the 1-dimensional 8mL2 Schrödinger equation allows for the calculation of energy levels in model systems. In some instances, if the architecture of the molecule is simple enough, it provides a high-quality estimate 4h2 8mL2 of the actual transition energies observed experimentally. Corrections to the equation and the addition of a temporal component of the h2 8mL2 equation make it even more powerful, but will not be described in this course. 0 L 0 L The three-dimensional time-independent Schrödinger equation can be solved in a ready manner using the separation of variables technique. Furthermore, solving for the energy of the system when implemented into a “particle in a box” type of scenario is rather straightforward. If the lengths of all of the 3 sides of the box are equivalent, degenerate energy levels appear as a natural consequence of quantum mechanics. Next Time: The Fermi Energy and the Density of States .
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