交换积分与成键积分计算及其在分子结构中应用.pdfVIP

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2.H:交换积分(β积分）

ab

$$\mathrm{H}_{\mathrm{ab}}=\int\psi_{\mathrm{a}}^{*}\hat{\mathrm{H}}\psi_

{\mathrm{b}}\mathrm{d}\tau=\a$$

$$\begin{array}{l}\a=\int\psi_{a}^{*}\hat{H}\psi_{b}d\tau=\int\psi_{a}^{*}

\left[-\frac{1}{2}\nabla^{2}-\frac{1}{r_{b}}-\frac{1}{r_{a}}+\frac{1}{R}\right]

\psi_{b}d\tau\\=E_{H}S_{ab}+\frac{1}{R}S_{ab}-\int\frac{1}{r_{a}}\psi_{a}

^{*}\psi_{b}d\tau=