Marcus Theory: Electron Transfer

Barrier ΔG‡
Rate k_ET (s⁻¹)
ln(k_ET)
Regime
Normal region
Marcus (1956, Nobel 1992): k_ET = (2π/ℏ)|H_DA|²/√(4πλk_BT) · exp[−(ΔG°+λ)²/(4λk_BT)]

Barrier: ΔG‡ = (ΔG°+λ)²/(4λ). Rate increases with |ΔG°| until ΔG°=−λ (barrierless), then decreases: inverted region.