量子力学第九弹——微扰论

最新推荐文章于 2023-06-15 17:47:19 发布

东门之杨

最新推荐文章于 2023-06-15 17:47:19 发布

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文章标签：量子力学微扰论

本文链接：https://blog.csdn.net/u013795675/article/details/45741833

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Nondegenerate case

H^| ψ n ⟩ = E n | ψ n ⟩

$\hat H|\psi_n\rangle=E_n|\psi_n\rangle$
Our purpose is to verify the value of

En $E_n$ and

|ψn⟩ $|\psi_n\rangle$
We expand them in a set of basis,

H^0 | ψ (0) m ⟩ = E (0) m | ψ (0) m ⟩

$\hat H_0|\psi_m^{(0)}\rangle=E_m^{(0)}|\psi_m^{(0)}\rangle$
Thus

⎧ ⎩ ⎨ ⎪ ⎪ ⎪ ⎪ E n = λ 0 E (0) n + λ 1 E (1) n + λ 2 E (2) n + \dots | ψ n ⟩ = \sum m C m | ψ (0) m ⟩ C m = λ 0 C (0) m + λ 1 C (1) m + λ 2 C (2) m + \dots

$\begin{cases}E_n=\lambda^0E_n^{(0)}+\lambda^1E_n^{(1)}+\lambda^2E_n^{(2)}+\cdots\\|\psi_n\rangle=\sum_mC_m|\psi_m^{(0)}\rangle\\C_m=\lambda^0C_m^{(0)}+\lambda^1C_m^{(1)}+\lambda^2C_m^{(2)}+\cdots\end{cases}$

Let $\hat H=\hat H_0+\lambda\hat W,$ and premultify the original equation with a random component of the basis.

$⟨ ψ (0) k | H^| ψ n ⟩ = ⟨ ψ (0) k | E n | ψ n ⟩$ $\langle \psi_k^{(0)}|\hat H|\psi_n\rangle=\langle \psi_k^{(0)}|E_n|\psi_n\rangle$
$l . h . s = = = = = = = = ⟨ ψ (0) k | H | ψ n ⟩ ⟨ ψ (0) k | H 0 + λ W | ψ n ⟩ ⟨ ψ (0) k | (H 0 + λ W) (\sum m | ψ (0) m ⟩ ⟨ ψ (0) m |) | ψ n ⟩ ⟨ ψ (0) k | H 0 (\sum m | ψ (0) m ⟩ ⟨ ψ (0) m |) | ψ n ⟩ + λ ⟨ ψ (0) k | W (\sum m | ψ (0) m ⟩ ⟨ ψ (0) m |) | ψ n ⟩ \sum m E (0) n δ m k C m + λ \sum m W k m C m E (0) n C k + λ \sum m W k m C m E (0) n (λ 0 C (0) k + λ 1 C (1) k + λ 2 C (2) k + \dots) + λ \sum m W k m (λ 0 C (0) m + λ 1 C (1) m + λ 2 C (2) m + \dots) λ 0 (E (0) n C (0) k) + λ 1 (E (0) n C (1) k + \sum m W k m C (0) m) + λ 2 (E (0) n C (2) k + \sum m W k m C (1) m) + \dots$ $\begin{align}l.h.s=&\langle \psi_k^{(0)}|H|\psi_n\rangle\\=&\langle \psi_k^{(0)}| H_0+\lambda W|\psi_n\rangle\\=&\langle \psi_k^{(0)}|( H_0+\lambda W)\left(\sum_m|\psi_m^{(0)}\rangle\langle\psi_m^{(0)}|\right)|\psi_n\rangle\\=&\langle \psi_k^{(0)}| H_0\left(\sum_m|\psi_m^{(0)}\rangle\langle\psi_m^{(0)}|\right)|\psi_n\rangle+\lambda\langle \psi_k^{(0)}| W\left(\sum_m|\psi_m^{(0)}\rangle\langle\psi_m^{(0)}|\right)|\psi_n\rangle\\=&\sum_mE_n^{(0)}\delta_{mk}C_m+\lambda\sum_m W_{km}C_m\\=&E_n^{(0)}C_k+\lambda\sum_m W_{km}C_m\\=&E_n^{(0)}(\lambda^0C_k^{(0)}+\lambda^1C_k^{(1)}+\lambda^2C_k^{(2)}+\cdots)+\lambda\sum_m W_{km}(\lambda^0C_m^{(0)}+\lambda^1C_m^{(1)}+\lambda^2C_m^{(2)}+\cdots)\\=&\lambda^0(E_n^{(0)}C_k^{(0)})+\lambda^1(E_n^{(0)}C_k^{(1)}+\sum_m W_{km}C_m^{(0)})+\lambda^2(E_n^{(0)}C_k^{(2)}+\sum_m W_{km}C_m^{(1)})+\cdots \end{align}$
$r . h . s = = = = ⟨ ψ (0) k | E n | ψ n ⟩ E n C k (λ 0 E (0) n + λ 1 E (1) n + λ 2 E (2) n + \dots) (λ 0 C (0) k + λ 1 C (1) k + λ 2 C (2) k + \dots) λ 0 (E (0) n C (0) k) + λ 1 (E (0) n C (1) k + E (1) n C (0) k) + λ 2 (E (0) n C (2) k + E (1) n C (1) k + E (2) n C (0) k) + \dots$ $\begin{align}r.h.s=&\langle \psi_k^{(0)}|E_n|\psi_n\rangle\\=&E_n C_k\\=&(\lambda^0E_n^{(0)}+\lambda^1E_n^{(1)}+\lambda^2E_n^{(2)}+\cdots)(\lambda^0C_k^{(0)}+\lambda^1C_k^{(1)}+\lambda^2C_k^{(2)}+\cdots)\\=&\lambda^0(E_n^{(0)}C_k^{(0)})+\lambda^1(E_n^{(0)}C_k^{(1)}+E_n^{(1)}C_k^{(0)})+\lambda^2(E_n^{(0)}C_k^{(2)}+E_n^{(1)}C_k^{(1)}+E_n^{(2)}C_k^{(0)})+\cdots \end{align}$
Compare coefficient

$\lambda^0\qquad E_k^{(0)}C_k^{(0)}=E_n^{(0)}C_k^{(0)}\Rightarrow C_k^{(0)}=\delta_{nk}$
$\lambda^1\qquad E_k^{(0)}C_k^{(1)}+\sum_m W_{km}C_m^{(0)}=E_n^{(0)}C_k^{(1)}+E_n^{(1)}C_k^{(0)}$

Let $k=n$
$\Rightarrow E (1) n = \sum m W n m C (0) m = \sum m W n m δ m n = W n n$ $\Rightarrow E_n^{(1)}=\sum_mW_{nm}C_m^{(0)}=\sum_mW_{nm}\delta_{mn}=W_{nn}$ Substitute in last equation $\Rightarrow C (1) k = W n k E ( 0 ) n - E ( 0 ) k (n \neq k)$ $\Rightarrow C_k^{(1)}=\dfrac{W_{nk}}{E_n^{(0)}-E_k^{(0)}}(n\ne k)$
$\lambda^2\qquad E_k^{(0)}C_k^{(2)}+\sum_m W_{km}C_m^{(1)}=E_n^{(0)}C_k^{(2)}+E_n^{(1)}C_k^{(1)}+E_n^{(2)}C_k^{(0)}$

Let $k=n$
$\Rightarrow E (2) n = \sum m \neq n | W n m | 2 E ( 0 ) n - E ( 0 ) k$ $\Rightarrow E_n^{(2)}=\sum_{m\ne n}\frac{|W_{nm}|^2}{E_n^{(0)}-E_k^{(0)}}$

最终解（能量近似到二阶，波函数近似到一阶）

$⎧ ⎩ ⎨ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ ⎪ E n | ψ n ⟩ = E (0) n + λ E (1) n + λ 2 E (2) n = E (0) n + H' n n + \sum m \neq n | H ' n m | E ( 0 ) n - E ( 0 ) m = \sum k (C (0) k + λ C (1) k) | ψ (0) k ⟩ = | ψ (0) k ⟩ + \sum k \neq n H ' k n E ( 0 ) n - E ( 0 ) k$ $\begin{cases}E_n&=E_n^{(0)}+\lambda E_n^{(1)}+\lambda^2 E_n^{(2)} \\&=E_n^{(0)}+H'_{nn}+\sum_{m\ne n}\frac{|H'_{nm}|}{E_n^{(0)}-E_m^{(0)}}\\|\psi_n\rangle &= \sum_{k}\left(C_k^{(0)}+\lambda C_k^{(1)}\right)|\psi_k^{(0)}\rangle\\&=|\psi_k^{(0)}\rangle+\sum_{k\ne n}\frac{H'_{kn}}{E_n^{(0)}-E_k^{(0)}}\end{cases}$

Degenerate Case

H^| ψ n ⟩ = E n | ψ n ⟩

$\hat H|\psi_n\rangle=E_n|\psi_n\rangle$
Our purpose is to verify the value of

En $E_n$ and

|ψn⟩ $|\psi_n\rangle$
We expand them in a set of basis,

H^0 | k ν ⟩ = E (0) k | k ν ⟩, ν = 1, 2, \dots, f k

$\hat H_0|k\nu\rangle=E_k^{(0)}|k\nu\rangle,\nu=1,2,\cdots,f_k$
Thus

⎧ ⎩ ⎨ ⎪ ⎪ E n = λ 0 E (0) n + λ 1 E (1) n + λ 2 E (2) n + \dots | ψ n ⟩ = \sum k ν C k ν | k ν ⟩ C k ν = λ 0 C (0) k ν + λ 1 C (1) k ν + λ 2 C (2) k ν + \dots

$\begin{cases}E_n=\lambda^0E_n^{(0)}+\lambda^1E_n^{(1)}+\lambda^2E_n^{(2)}+\cdots\\|\psi_n\rangle=\sum_{k\nu}C_{k\nu}|k\nu\rangle\\C_{k\nu}=\lambda^0C_{k\nu}^{(0)}+\lambda^1C_{k\nu}^{(1)}+\lambda^2C_{k\nu}^{(2)}+\cdots\end{cases}$

Let $\hat H=\hat H_0+\lambda\hat W,$ and premultify the original equation with a random component of the basis.

$⟨ m μ | H^| ψ n ⟩ = ⟨ m μ | E n | ψ n ⟩$ $\langle m\mu|\hat H|\psi_n\rangle=\langle m\mu|E_n|\psi_n\rangle$
$l . h . s = = = = = = = = ⟨ m μ | H | ψ n ⟩ ⟨ m μ | H 0 + λ W | ψ n ⟩ ⟨ m μ | (H 0 + λ W) ⎛ ⎝ \sum k, v | k ν ⟩ ⟨ k ν | ⎞ ⎠ | ψ n ⟩ ⟨ m μ | H 0 ⎛ ⎝ \sum k, v | k ν ⟩ ⟨ k ν | ⎞ ⎠ | ψ n ⟩ + λ ⟨ m μ | W ⎛ ⎝ \sum k, ν | k ν ⟩ ⟨ k ν | ⎞ ⎠ | ψ n ⟩ \sum k, ν E (0) m δ m k δ μ ν C k ν + λ \sum k, ν W m μ, k ν C k ν E (0) m C m μ + λ \sum k, ν W m μ, k ν C k ν E (0) m (λ 0 C (0) m μ + λ 1 C (1) m μ + λ 2 C (2) m μ + \dots) + λ \sum k, ν W m μ, k ν (λ 0 C (0) k ν + λ 1 C (1) k ν + λ 2 C (2) k ν + \dots) λ 0 (E (0) m C (0) m μ) + λ 1 (E (0) m C (1) m μ + \sum k, ν W m μ, k ν C (0) k ν) + λ 2 (E (0) m C (2) m μ + \sum k, ν W m μ, k ν C (1) k ν) + \dots$ $\begin{align}l.h.s=&\langle m\mu|H|\psi_n\rangle\\=&\langle m\mu| H_0+\lambda W|\psi_n\rangle\\=&\langle m\mu|( H_0+\lambda W)\left(\sum_{k,v}|k\nu\rangle\langle k\nu|\right)|\psi_n\rangle\\=&\langle m\mu| H_0\left(\sum_{k,v}|k\nu\rangle\langle k\nu|\right)|\psi_n\rangle+\lambda\langle m\mu| W\left(\sum_{k,\nu}|k\nu\rangle\langle k\nu|\right)|\psi_n\rangle\\=&\sum_{k,\nu}E_m^{(0)}\delta_{mk}\delta_{\mu\nu}C_{k\nu}+\lambda\sum_{k,\nu}W_{m\mu,k\nu}C_{k\nu}\\=&E_m^{(0)}C_{m\mu}+\lambda\sum_{k,\nu} W_{m\mu,k\nu}C_{k\nu}\\=&E_m^{(0)}(\lambda^0C_{m\mu}^{(0)}+\lambda^1C_{m\mu}^{(1)}+\lambda^2C_{m\mu}^{(2)}+\cdots)+\lambda\sum_{k,\nu} W_{m\mu,k\nu}(\lambda^0C_{k\nu}^{(0)}+\lambda^1C_{k\nu}^{(1)}+\lambda^2C_{k\nu}^{(2)}+\cdots)\\=&\lambda^0(E_m^{(0)}C_{m\mu}^{(0)})+\lambda^1(E_m^{(0)}C_{m\mu}^{(1)}+\sum_{k,\nu} W_{m\mu,k\nu}C_{k\nu}^{(0)})+\lambda^2(E_m^{(0)}C_{m\mu}^{(2)}+\sum_{k,\nu} W_{m\mu,k\nu}C_{k\nu}^{(1)})+\cdots \end{align}$
$r . h . s = = = = ⟨ m μ | E n | ψ n ⟩ E n C m μ (λ 0 E (0) n + λ 1 E (1) n + λ 2 E (2) n + \dots) (λ 0 C (0) k + λ 1 C (1) m μ + λ 2 C (2) m μ + \dots) λ 0 (E (0) n C (0) m μ) + λ 1 (E (0) n C (1) m μ + E (1) n C (0) m μ) + λ 2 (E (0) n C (2) m μ + E (1) n C (1) m μ + E (2) n C (0) m μ) + \dots$ $\begin{align}r.h.s=&\langle m\mu|E_n|\psi_n\rangle\\=&E_n C_{m\mu}\\=&(\lambda^0E_n^{(0)}+\lambda^1E_n^{(1)}+\lambda^2E_n^{(2)}+\cdots)(\lambda^0C_k^{(0)}+\lambda^1C_{m\mu}^{(1)}+\lambda^2C_{m\mu}^{(2)}+\cdots)\\=&\lambda^0(E_n^{(0)}C_{m\mu}^{(0)})+\lambda^1(E_n^{(0)}C_{m\mu}^{(1)}+E_n^{(1)}C_{m\mu}^{(0)})+\lambda^2(E_n^{(0)}C_{m\mu}^{(2)}+E_n^{(1)}C_{m\mu}^{(1)}+E_n^{(2)}C_{m\mu}^{(0)})+\cdots \end{align}$
Compare coefficient

$\lambda^0\qquad E_m^{(0)}C_{m\mu}^{(0)}=E_n^{(0)}C_{m\mu}^{(0)}\Rightarrow C_{m\mu}^{(0)}=a_{\mu}\delta_{nm}$
$\lambda^1\qquad E_m^{(0)}C_{m\mu}^{(1)}+\sum_m W_{m\mu,k\nu}C_{k\nu}^{(0)}=E_n^{(0)}C_{m\mu}^{(1)}+E_n^{(1)}C_{m\mu}^{(0)}$

Let $m=n$
$\Rightarrow E (1) n \cdot a μ = \sum n W n μ, k ν C (0) n = \sum n W n μ, k ν \cdot a ν δ k n = \sum n W n μ, n ν a ν$ $\Rightarrow E_n^{(1)}\cdot a_{\mu}=\sum_nW_{n\mu,k\nu}C_n^{(0)}=\sum_nW_{n\mu,k\nu}\cdot a_{\nu}\delta_{kn}=\sum_nW_{n\mu,n\nu}a_{\nu}$ Difine $W μ ν = W n μ, n ν$ $W_{\mu\nu}=W_{n\mu,n\nu}$ Then $\sum ν (W μ ν - E (1) n δ μ ν) = 0$ $\sum_{\nu}\left(W_{\mu\nu}-E_n^{(1)}\delta_{\mu\nu}\right)=0$ $\Rightarrow det | W μ ν - E (1) n δ μ ν | = 0$ $\Rightarrow \det|W_{\mu\nu}-E_n^{(1)}\delta_{\mu\nu}|=0$ The above equation about $E_n^{(1)}$ has $f_n$ 个根 $E (1) n = E (1) n α, α = 1, 2, \dots, f n a ν = a α ν$ $E_n^{(1)}=E_{n\alpha}^{(1)},\alpha=1,2,\cdots,f_n \\ a_{\nu}=a_{\alpha\nu}$ $\Rightarrow {| ψ n α = \sum f n ν = 1 a α ν | k ν ⟩ E n = E (0) n + λ E (1) n α, α = 1, 2, \dots, f n$ $\Rightarrow \begin{cases}|\psi_{n\alpha}=\sum_{\nu=1}^{f_n}a_{\alpha\nu}|k\nu\rangle\\E_n=E_n^{(0)}+\lambda E_{n\alpha}^{(1)},\alpha=1,2,\cdots,f_n\end{cases}$
这样原来简并的能级可能出现部分消除或者全部消除。