目錄
1 引言
在《量子力學》1這本書中,其中一節的內容就是關於「一維諧振子」的定態 Schrödinger 方程2。內容如下﹕
一維諧振子的勢場 V ( x ) = 1 2 m ω 2 x 2 V(x) = \frac{1}{2}m\omega^2x^2 V(x)=21mω2x2
其定態波函數 ψ ( x ) \psi(x) ψ(x) 滿足 − ℏ 2 2 m d 2 ψ d x 2 + 1 2 m ω 2 x 2 ψ = E ψ -\frac{\hbar^2}{2m}\frac{d^2 \psi}{dx^2}+\frac{1}{2}m\omega^2x^2\psi=E\psi −2mℏ2dx2d2ψ+21mω2x2ψ=Eψ
解方程後得 ψ n ( x ) = N n exp ( − α 2 x 2 2 ) H n ( α x ) \psi_n(x)=N_n\exp(-\frac{\alpha^2x^2}{2})H_n(\alpha x) ψn(x)=Nnexp(−2α2x2)Hn(αx)N n N_n Nn 是歸一化因子 α π 1 2 ⋅ 2 n ⋅ n ! \sqrt{\frac{\alpha}{\pi^{\frac{1}{2}}\cdot 2^n\cdot n!}} π21⋅2n⋅n!α
α \alpha α 是位移無量綱化因子 m ω ℏ \sqrt{\frac{m\omega}{\hbar}} ℏmω
H n ( x ) H_n(x) Hn(x) 是 n n n 階 Hermite 多項式 ( − 1 ) n exp ( x 2 ) d n d x n exp ( − x 2 ) (-1)^n\exp(x^2)\frac{d^n}{dx^n}\exp(-x^2) (−1)nexp(x2)dxndnexp(−x2)
E n E_n En 是粒子能級分佈 ( n + 1 2 ) ℏ ω (n+\frac{1}{2})\hbar\omega (n+21)ℏω。
我基於一維諧振子的理論,延伸到二維諧振子,逐步延伸 n 維諧振子,然後由二維諧振子延伸到二維「正定勢場」下的波函數,最後擴展到 n 維空間「正定勢場」下的波函數。
2 二維諧振子
二維諧振子下的勢場
V
(
x
,
y
)
=
1
2
m
ω
2
(
x
2
+
y
2
)
V(x,y)=\frac{1}{2}m\omega^2(x^2+y^2)
V(x,y)=21mω2(x2+y2)
其定態波函數
ψ
(
x
,
y
)
\psi(x,y)
ψ(x,y) 滿足
−
ℏ
2
2
m
∇
2
ψ
(
x
,
y
)
+
1
2
m
ω
2
(
x
2
+
y
2
)
ψ
(
x
,
y
)
=
E
ψ
(
x
,
y
)
-\frac{\hbar^2}{2m}\nabla^2\psi(x,y)+\frac{1}{2}m\omega^2(x^2+y^2)\psi(x,y)=E\psi(x,y)
−2mℏ2∇2ψ(x,y)+21mω2(x2+y2)ψ(x,y)=Eψ(x,y)
定義算子
H
x
^
=
−
ℏ
2
2
m
∂
2
∂
x
2
+
1
2
m
ω
2
x
2
\hat{H_x}=-\frac{\hbar^2}{2m}\frac{\partial^2}{\partial x^2}+\frac{1}{2}m\omega^2x^2
Hx^=−2mℏ2∂x2∂2+21mω2x2
H
y
^
=
−
ℏ
2
2
m
∂
2
∂
y
2
+
1
2
m
ω
2
y
2
\hat{H_y}=-\frac{\hbar^2}{2m}\frac{\partial^2}{\partial y^2}+\frac{1}{2}m\omega^2y^2
Hy^=−2mℏ2∂y2∂2+21mω2y2
利用分離變量法,設
ψ
(
x
,
y
)
=
f
(
x
)
g
(
y
)
\psi(x,y)=f(x)g(y)
ψ(x,y)=f(x)g(y),所以有
H
^
ψ
=
g
(
y
)
H
x
^
f
(
x
)
+
f
(
x
)
H
y
^
g
(
y
)
=
E
f
(
x
)
g
(
y
)
f
(
x
)
H
y
^
g
(
y
)
=
(
E
f
(
x
)
−
H
x
^
f
(
x
)
)
g
(
y
)
H
y
^
g
(
y
)
=
E
y
g
(
y
)
且
H
x
^
f
(
x
)
)
=
(
E
−
E
y
)
f
(
x
)
=
E
x
f
(
x
)
\hat{H}\psi=g(y)\hat{H_x}f(x)+f(x)\hat{H_y}g(y)=Ef(x)g(y)\\[1em] f(x)\hat{H_y}g(y)=(Ef(x)-\hat{H_x}f(x))g(y)\\[1em] \hat{H_y}g(y)=E_yg(y)\ \text{且}\ \hat{H_x}f(x))=(E-E_y)f(x)=E_xf(x)
H^ψ=g(y)Hx^f(x)+f(x)Hy^g(y)=Ef(x)g(y)f(x)Hy^g(y)=(Ef(x)−Hx^f(x))g(y)Hy^g(y)=Eyg(y) 且 Hx^f(x))=(E−Ey)f(x)=Exf(x)
由一維諧振子的結論可得,
H
x
^
\hat{H_x}
Hx^ 和
H
y
^
\hat{H_y}
Hy^ 的本征值都是
{
E
1
,
n
}
n
≥
0
\{E_{1,n}\}_{n\geq0}
{E1,n}n≥0,對應的本征函數是
{
ψ
n
(
x
)
}
n
≥
0
\{\psi_n(x)\}_{n\geq0}
{ψn(x)}n≥0 和
{
ψ
n
(
y
)
}
n
≥
0
\{\psi_n(y)\}_{n\geq0}
{ψn(y)}n≥0。
現在
f
f
f 和
g
g
g 分別是
H
x
^
\hat{H_x}
Hx^ 和
H
y
^
\hat{H_y}
Hy^ 的本征函數,所以
f
∈
{
ψ
n
(
x
)
}
n
≥
0
f \in \{\psi_n(x)\}_{n\geq0}
f∈{ψn(x)}n≥0 和
g
∈
{
ψ
n
(
y
)
}
n
≥
0
g \in \{\psi_n(y)\}_{n\geq0}
g∈{ψn(y)}n≥0,即
ψ
m
+
n
(
x
,
y
)
=
ψ
m
(
x
)
ψ
n
(
y
)
\psi_{m+n}(x,y)=\psi_m(x)\psi_n(y)
ψm+n(x,y)=ψm(x)ψn(y)。與此同時,對應的能級是
E
2
,
N
=
E
m
n
=
E
1
,
m
+
E
1
,
n
=
(
m
+
n
+
1
)
ℏ
ω
E_{2,N}=E_{mn}=E_{1,m}+E_{1,n}=(m+n+1)\hbar\omega
E2,N=Emn=E1,m+E1,n=(m+n+1)ℏω,簡並度是
(
N
+
1
1
)
=
N
+
1
\left(\begin{matrix}N+1\\1\end{matrix}\right)=N+1
(N+11)=N+1。
3 n n n 維諧振子
以下用數學歸納法來證明如下命題﹕
當 n n n 維諧振子的勢場為 V ( r n ⃗ ) = V ( x 1 , x 2 , ⋯ , x n ) = 1 2 m ω 2 r n ⃗ 2 V(\vec{r_n}) = V(x_1,x_2,\cdots,x_n) = \frac{1}{2}m\omega^2\vec{r_n}^2 V(rn)=V(x1,x2,⋯,xn)=21mω2rn2,
本征波函數族為 { ∏ k = 1 n ψ N k ( x k ) ∣ ∑ k = 1 n N k = N } \{\prod\limits_{k=1}^{n}\psi_{N_k}(x_k)|\sum\limits_{k=1}^{n}N_k=N\} {k=1∏nψNk(xk)∣k=1∑nNk=N},其中 ψ k \psi_k ψk 是一維諧振子各能級 E k E_k Ek 對應的定態波函數。與此同時,對應的本征能級是 E n , N = ( ∑ k = 1 n N k + n 2 ) ℏ ω = ( N + n 2 ) ℏ ω E_{n,N}=(\sum\limits_{k=1}^nN_k+\frac{n}{2})\hbar\omega=(N+\frac{n}{2})\hbar\omega En,N=(k=1∑nNk+2n)ℏω=(N+2n)ℏω,簡並度是 ( N + n − 1 n − 1 ) \left(\begin{matrix}N+n-1\\n-1\end{matrix}\right) (N+n−1n−1)
(1.) 當
n
=
1
n = 1
n=1 時,命題等價於一維諧振子結論
(2.) 假設
n
=
t
−
1
n = t - 1
n=t−1 時命題成立,那麼當
n
=
t
n = t
n=t 時,設
ψ
(
r
t
⃗
)
=
ψ
(
r
t
−
1
→
,
x
t
)
=
f
(
r
t
−
1
→
)
g
(
x
t
)
\psi(\vec{r_t})=\psi(\overrightarrow{r_{t-1}},x_t) = f(\overrightarrow{r_{t-1}})g(x_t)
ψ(rt)=ψ(rt−1,xt)=f(rt−1)g(xt)。
記
∇
r
t
−
1
→
2
=
∑
i
=
1
t
−
1
∂
2
∂
x
i
2
H
r
t
−
1
→
^
=
−
ℏ
2
2
m
∇
r
t
−
1
→
2
+
1
2
m
ω
2
r
t
1
→
2
H
x
t
^
=
−
ℏ
2
2
m
∂
2
∂
x
t
2
+
1
2
m
ω
2
x
t
2
\nabla_{\overrightarrow{r_{t-1}}}^2=\sum_{i=1}^{t-1}\frac{\partial^2}{\partial x_i^2}\\[1em] \hat{H_{\overrightarrow{r_{t-1}}}}=-\frac{\hbar^2}{2m}\nabla_{\overrightarrow{r_{t-1}}}^2+\frac{1}{2}m\omega^2\overrightarrow{r_{t_1}}^2\\[1em] \hat{H_{x_t}}=-\frac{\hbar^2}{2m}\frac{\partial^2}{\partial x_t^2}+\frac{1}{2}m\omega^2x_t^2
∇rt−12=i=1∑t−1∂xi2∂2Hrt−1^=−2mℏ2∇rt−12+21mω2rt12Hxt^=−2mℏ2∂xt2∂2+21mω2xt2
所以
H
^
=
−
ℏ
2
2
m
∇
r
t
→
2
+
1
2
m
ω
2
r
t
→
2
=
(
−
ℏ
2
2
m
∇
r
t
−
1
→
2
+
1
2
m
ω
2
r
t
1
→
2
)
+
(
−
ℏ
2
2
m
∂
2
∂
x
t
2
+
1
2
m
ω
2
x
t
2
)
=
H
r
t
−
1
→
^
+
H
x
t
^
\hat{H}=-\frac{\hbar^2}{2m}\nabla_{\overrightarrow{r_t}}^2+\frac{1}{2}m\omega^2\overrightarrow{r_t}^2=\left(-\frac{\hbar^2}{2m}\nabla_{\overrightarrow{r_{t-1}}}^2+\frac{1}{2}m\omega^2\overrightarrow{r_{t_1}}^2\right)+\left(-\frac{\hbar^2}{2m}\frac{\partial^2}{\partial x_t^2}+\frac{1} {2}m\omega^2x_t^2\right)=\hat{H_{\overrightarrow{r_{t-1}}}}+\hat{H_{x_t}}
H^=−2mℏ2∇rt2+21mω2rt2=(−2mℏ2∇rt−12+21mω2rt12)+(−2mℏ2∂xt2∂2+21mω2xt2)=Hrt−1^+Hxt^
利用分離變量法,設
ψ
(
r
t
→
)
=
f
(
r
t
−
1
→
)
g
(
r
t
)
\psi(\overrightarrow{r_t})=f(\overrightarrow{r_{t-1}})g(r_t)
ψ(rt)=f(rt−1)g(rt),類似二維諧振子般,可以得到如下關係式
H
x
t
^
g
(
y
)
=
E
x
t
g
(
x
t
)
且
H
r
t
−
1
→
^
f
(
r
t
−
1
→
)
)
=
(
E
−
E
x
t
)
f
(
r
t
−
1
→
)
=
E
r
t
−
1
→
f
(
r
t
−
1
→
)
\hat{H_{x_t}}g(y)=E_{x_t}g(x_t)\ \text{且}\ \hat{H_{\overrightarrow{r_{t-1}}}}f(\overrightarrow{r_{t-1}}))=(E-E_{x_t})f(\overrightarrow{r_{t-1}})=E_{\overrightarrow{r_{t-1}}}f(\overrightarrow{r_{t-1}})
Hxt^g(y)=Extg(xt) 且 Hrt−1^f(rt−1))=(E−Ext)f(rt−1)=Ert−1f(rt−1)
由 (1.) 知,
H
x
t
^
\hat{H_{x_t}}
Hxt^ 的本征值是
{
E
1
,
N
}
N
≥
0
=
{
(
N
+
1
2
)
ℏ
ω
}
N
≥
0
\{E_{1,N}\}_{N\geq0}=\{(N+\frac{1}{2})\hbar\omega\}_{N\geq0}
{E1,N}N≥0={(N+21)ℏω}N≥0,對應的本征函數是
{
ψ
N
(
x
t
)
}
N
≥
0
\{\psi_N(x_t)\}_{N\geq0}
{ψN(xt)}N≥0。
由歸納假設知,
H
r
t
−
1
→
^
\hat{H_{\overrightarrow{r_{t-1}}}}
Hrt−1^ 的本征值是
{
E
t
−
1
,
N
}
N
≥
0
=
{
(
N
+
t
−
1
2
)
ℏ
ω
}
n
≥
0
\{E_{t-1,N}\}_{N\geq0}=\{(N+\frac{t-1}{2})\hbar\omega\}_{n\geq0}
{Et−1,N}N≥0={(N+2t−1)ℏω}n≥0,每一個本征值
E
t
−
1
,
N
E_{t-1,N}
Et−1,N 對應的本征函數族是
{
∏
k
=
1
t
−
1
ψ
N
k
(
x
k
)
∣
∑
k
=
1
t
−
1
N
k
=
N
}
\{\prod\limits_{k=1}^{t-1}\psi_{N_k}(x_k)|\sum\limits_{k=1}^{t-1}N_k=N\}
{k=1∏t−1ψNk(xk)∣k=1∑t−1Nk=N}
因此,
H
^
\hat{H}
H^ 的本征值便是
{
E
t
,
N
}
N
≥
0
=
{
E
t
−
1
,
N
+
E
1
,
0
}
N
≥
0
=
{
(
N
+
t
−
1
2
+
0
+
1
2
)
ℏ
ω
}
N
≥
0
=
{
(
N
+
t
2
)
}
N
≥
0
\{E_{t,N}\}_{N\geq0}=\{E_{t-1,N}+E_{1,0}\}_{N\geq0}=\{(N+\frac{t-1}{2}+0+\frac{1}{2})\hbar\omega\}_{N\geq0}=\{(N+\frac{t}{2})\}_{N\geq0}
{Et,N}N≥0={Et−1,N+E1,0}N≥0={(N+2t−1+0+21)ℏω}N≥0={(N+2t)}N≥0,對應的本征值函數族是
{
∏
k
=
1
t
ψ
N
k
(
x
k
)
∣
∑
k
=
1
t
N
k
=
N
}
\{\prod\limits_{k=1}^{t}\psi_{N_k}(x_k)|\sum\limits_{k=1}^{t}N_k=N\}
{k=1∏tψNk(xk)∣k=1∑tNk=N}
結合(1.) 和 (2.),根據數學歸納原理可知,原命題對於任意正整數 n n n 皆成立。
4 二維「正定勢場」下的定態 Schrödinger 方程
我先不引入「正定勢場」的概念,而是用另一個特殊勢場作為引入,求解其定態 Schrödinger 方程。
V
(
x
,
y
)
=
1
2
m
ω
2
(
x
2
+
x
y
+
y
2
)
V(x,y)=\frac{1}{2}m\omega^2(x^2+xy+y^2)
V(x,y)=21mω2(x2+xy+y2)
考慮座標變換(讀者可以先自行思考)
(
u
v
)
=
(
1
2
1
2
1
2
−
1
2
)
(
x
y
)
\left( \begin{matrix} u\\ v \end{matrix} \right)= \left( \begin{matrix} \frac{1}{\sqrt{2}} & \frac{1}{\sqrt{2}}\\ \frac{1}{\sqrt{2}} & -\frac{1}{\sqrt{2}} \end{matrix} \right) \left( \begin{matrix} x\\ y \end{matrix} \right)
(uv)=(212121−21)(xy)
用
u
u
u、
v
v
v 表示
∇
2
\nabla^2
∇2﹕
∂
∂
x
=
∂
∂
u
∂
u
∂
x
+
∂
∂
v
∂
v
∂
x
=
1
2
(
∂
∂
u
+
∂
∂
v
)
∂
2
∂
x
2
=
1
2
(
∂
∂
u
+
∂
∂
v
)
⋅
1
2
(
∂
∂
u
+
∂
∂
v
)
=
1
2
(
∂
2
∂
u
2
+
∂
2
∂
v
2
+
∂
2
∂
u
∂
v
+
∂
2
∂
v
∂
u
)
\frac{\partial}{\partial x}=\frac{\partial}{\partial u}\frac{\partial u}{\partial x}+\frac{\partial}{\partial v}\frac{\partial v}{\partial x}=\frac{1}{\sqrt{2}}(\frac{\partial}{\partial u}+\frac{\partial}{\partial v})\\[1em] \frac{\partial^2}{\partial x^2}=\frac{1}{\sqrt{2}}(\frac{\partial}{\partial u}+\frac{\partial}{\partial v})\cdot\frac{1}{\sqrt{2}}(\frac{\partial}{\partial u}+\frac{\partial}{\partial v})=\frac{1}{2}(\frac{\partial^2}{\partial u^2}+\frac{\partial^2}{\partial v^2}+\frac{\partial^2}{\partial u\partial v}+\frac{\partial^2}{\partial v\partial u})
∂x∂=∂u∂∂x∂u+∂v∂∂x∂v=21(∂u∂+∂v∂)∂x2∂2=21(∂u∂+∂v∂)⋅21(∂u∂+∂v∂)=21(∂u2∂2+∂v2∂2+∂u∂v∂2+∂v∂u∂2)
同理可得
∂
2
∂
y
2
=
1
2
(
∂
2
∂
u
2
+
∂
2
∂
v
2
−
∂
2
∂
u
∂
v
−
∂
2
∂
v
∂
u
)
∇
2
=
∂
2
∂
x
2
+
∂
2
∂
y
2
=
∂
2
∂
u
2
+
∂
2
∂
v
2
\frac{\partial^2}{\partial y^2}=\frac{1}{2}(\frac{\partial^2}{\partial u^2}+\frac{\partial^2}{\partial v^2}-\frac{\partial^2}{\partial u\partial v}-\frac{\partial^2}{\partial v\partial u})\\[1em] \nabla^2=\frac{\partial^2}{\partial x^2}+\frac{\partial^2}{\partial y^2}=\frac{\partial^2}{\partial u^2}+\frac{\partial^2}{\partial v^2}
∂y2∂2=21(∂u2∂2+∂v2∂2−∂u∂v∂2−∂v∂u∂2)∇2=∂x2∂2+∂y2∂2=∂u2∂2+∂v2∂2
簡記
∇
x
y
2
=
∇
u
v
2
\nabla^2_{xy}=\nabla^2_{uv}
∇xy2=∇uv2
用
u
u
u、
v
v
v 改寫勢場﹕
V
=
1
2
m
ω
2
(
3
2
u
2
+
1
2
v
2
)
=
1
2
m
(
3
2
ω
)
2
u
2
+
1
2
m
(
1
2
ω
)
2
v
2
V=\frac{1}{2}m\omega^2(\frac{3}{2}u^2+\frac{1}{2}v^2)=\frac{1}{2}m(\sqrt{\frac{3}{2}}\omega)^2u^2+\frac{1}{2}m(\sqrt{\frac{1}{2}}\omega)^2v^2
V=21mω2(23u2+21v2)=21m(23ω)2u2+21m(21ω)2v2
記
H
x
,
ω
^
=
−
ℏ
2
2
m
∂
2
∂
x
2
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\hat{H_{x,\omega}}=-\frac{\hbar^2}{2m}\frac{\partial^2}{\partial x^2}+\frac{1}{2}m\omega^2x^2\\[1em] \psi_{\omega,n}(x)=\sqrt{\frac{\sqrt{\frac{m\omega}{\hbar}}}{\pi^{\frac{1}{2}}\cdot 2^n\cdot n!}}\exp(-\frac{\frac{m\omega}{\hbar}x^2}{2})H_n(\sqrt{\frac{m\omega}{\hbar}} x)
Hx,ω^=−2mℏ2∂x2∂2+21mω2x2ψω,n(x)=π21⋅2n⋅n!ℏmωexp(−2ℏmωx2)Hn(ℏmωx)
所以在這個勢場下的哈密頓算符是
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\hat{H}=\hat{H_{u,\sqrt{\frac{3}{2}}\omega}}+\hat{H_{v,\sqrt{\frac{1}{2}}\omega}}
H^=Hu,23ω^+Hv,21ω^
如二維諧振子般利用分離變量法,可得本征波函數
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\psi(x,y)=\psi_{\sqrt{\frac{3}{2}}\omega,m}(u)\psi_{\sqrt{\frac{1}{2}}\omega,n}(v)=\psi_{\sqrt{\frac{3}{2}}\omega,m}(\frac{x+y}{\sqrt{2}})\psi_{\sqrt{\frac{1}{2}}\omega,n}(\frac{x-y}{\sqrt{2}})
ψ(x,y)=ψ23ω,m(u)ψ21ω,n(v)=ψ23ω,m(2x+y)ψ21ω,n(2x−y)
對應的本征能級是
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E_{m,n}=\left[(m+\frac{1}{2})\sqrt{\frac{3}{2}}+(n+\frac{1}{2})\sqrt{\frac{1}{2}}\right]\hbar\omega
Em,n=[(m+21)23+(n+21)21]ℏω
顯然地,這個能級是非簡並的。
忽略能級簡並度的因素,我們去擴展這個問題﹕
如果勢函數 V ( x , y ) V(x,y) V(x,y) 可以寫成
V ( x , y ) = 1 2 m ω 2 ( x y ) ( a b b c ) ( x y ) V(x,y)=\frac{1}{2}m\omega^2\left(\begin{matrix}x&y\end{matrix}\right)\left(\begin{matrix}a&b\\b&c\end{matrix}\right)\left(\begin{matrix}x\\y\end{matrix}\right) V(x,y)=21mω2(xy)(abbc)(xy)
且當 ( x , y ) ≠ ( 0 , 0 ) (x,y) \neq (0,0) (x,y)=(0,0) 時 V ( x , y ) > 0 V(x,y) > 0 V(x,y)>0
那麼定態波函數 ψ ( x , y ) \psi(x,y) ψ(x,y) 是否可以寫成 ψ λ 1 ω , m ( k 1 x + b 1 y ) ⋅ ψ λ 2 ω , n ( k 2 x + b 2 y ) \psi_{\lambda_1\omega,m}(k_1x+b_1y)\cdot\psi_{\lambda_2\omega,n}(k_2x+b_2y) ψλ1ω,m(k1x+b1y)⋅ψλ2ω,n(k2x+b2y)的形式呢?(其中, k 1 , b 1 , k 2 , b 2 , λ 1 , λ 2 k_1,b_1,k_2,b_2,\lambda_1,\lambda_2 k1,b1,k2,b2,λ1,λ2 都是常數)
注意到矩陣
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\left(\begin{matrix}a&b\\b&c\end{matrix}\right)
(abbc) 是實對稱正定矩陣 (若讀者對正定矩陣不瞭解,可以參考 MIT 的 Introduction to Linear Algebra3 書籍),所以可以進行正交對角化。即存在一個正交矩陣
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Q=\left(\begin{matrix}q_{11}&q_{12}\\q_{21}&g_{22}\end{matrix}\right)
Q=(q11q21q12g22) 和一個對角矩陣
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\Lambda=diag(\lambda_1^2,\lambda_2^2)
Λ=diag(λ12,λ22),滿足
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A=Q^T\Lambda Q\\[1em] V(x,y)=\frac{1}{2}m\omega^2\left(\begin{matrix}x&y\end{matrix}\right)Q^T\Lambda Q\left(\begin{matrix}x\\y\end{matrix}\right)=\frac{1}{2}m\omega^2\vec{q}^T\Lambda \vec{q}=\frac{1}{2}m(\lambda_1\omega)^2u^2+\frac{1}{2}m(\lambda_2\omega)^2v^2
A=QTΛQV(x,y)=21mω2(xy)QTΛQ(xy)=21mω2qTΛq=21m(λ1ω)2u2+21m(λ2ω)2v2
此時,
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u=q_{11}x+q_{12}y
u=q11x+q12y、
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v=q21x+q22y
下面證明﹕
∂ 2 ∂ x 2 + ∂ 2 ∂ y 2 = ∂ 2 ∂ u 2 + ∂ 2 ∂ v 2 \frac{\partial^2}{\partial x^2}+ \frac{\partial^2}{\partial y^2}= \frac{\partial^2}{\partial u^2}+ \frac{\partial^2}{\partial v^2} ∂x2∂2+∂y2∂2=∂u2∂2+∂v2∂2
證﹕
∂ ∂ x = ∂ ∂ u ∂ u ∂ x + ∂ ∂ v ∂ v ∂ x = q 11 ∂ ∂ u + q 21 ∂ ∂ v ∂ 2 ∂ x 2 = ∂ ∂ x ⋅ ∂ ∂ x = ( q 11 ∂ ∂ u + q 21 ∂ ∂ v ) ( q 11 ∂ ∂ u + q 21 ∂ ∂ v ) = q 11 2 ∂ 2 ∂ u 2 + q 21 2 ∂ 2 ∂ u 2 + q 11 q 21 ( ∂ 2 ∂ u ∂ v + ∂ 2 ∂ v ∂ u ) \frac{\partial}{\partial x} = \frac{\partial}{\partial u}\frac{\partial u}{\partial x}+\frac{\partial}{\partial v}\frac{\partial v}{\partial x} = q_{11}\frac{\partial}{\partial u}+q_{21}\frac{\partial}{\partial v}\\[1em] \frac{\partial^2}{\partial x^2}=\frac{\partial}{\partial x} \cdot \frac{\partial}{\partial x}=(q_{11}\frac{\partial}{\partial u}+q_{21}\frac{\partial}{\partial v})(q_{11}\frac{\partial}{\partial u}+q_{21}\frac{\partial}{\partial v})=q_{11}^2\frac{\partial^2}{\partial u^2}+q_{21}^2\frac{\partial^2}{\partial u^2}+q_{11}q_{21}(\frac{\partial^2}{\partial u\partial v}+\frac{\partial^2}{\partial v\partial u}) ∂x∂=∂u∂∂x∂u+∂v∂∂x∂v=q11∂u∂+q21∂v∂∂x2∂2=∂x∂⋅∂x∂=(q11∂u∂+q21∂v∂)(q11∂u∂+q21∂v∂)=q112∂u2∂2+q212∂u2∂2+q11q21(∂u∂v∂2+∂v∂u∂2)
同理可得
∂ 2 ∂ y 2 = q 12 2 ∂ 2 ∂ u 2 + q 22 2 ∂ 2 ∂ u 2 + q 12 q 22 ( ∂ 2 ∂ u ∂ v + ∂ 2 ∂ v ∂ u ) \frac{\partial^2}{\partial y^2}=q_{12}^2\frac{\partial^2}{\partial u^2}+q_{22}^2\frac{\partial^2}{\partial u^2}+q_{12}q_{22}(\frac{\partial^2}{\partial u\partial v}+\frac{\partial^2}{\partial v\partial u}) ∂y2∂2=q122∂u2∂2+q222∂u2∂2+q12q22(∂u∂v∂2+∂v∂u∂2)
利用正交矩陣的定義
q 11 2 + q 12 2 = q 21 2 + q 22 2 = 1 q 11 q 21 + q 12 q 22 = 0 q_{11}^2+q_{12}^2=q_{21}^2+q_{22}^2=1\\[1em] q_{11}q_{21}+q_{12}q_{22}=0 q112+q122=q212+q222=1q11q21+q12q22=0
可證得
∂ 2 ∂ x 2 + ∂ 2 ∂ y 2 = ∂ 2 ∂ u 2 + ∂ 2 ∂ v 2 \frac{\partial^2}{\partial x^2}+ \frac{\partial^2}{\partial y^2}= \frac{\partial^2}{\partial u^2}+ \frac{\partial^2}{\partial v^2} ∂x2∂2+∂y2∂2=∂u2∂2+∂v2∂2
利用上方結論,可以得出算符量
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\hat{T}=\hat{T_u}+\hat{T_v}\\[1em] \hat{V}=\hat{V_{\lambda_1\omega}}+\hat{V_{\lambda_2\omega}}\\[1em] \hat{H}=\hat{H_{\lambda_1\omega,u}}+\hat{H_{\lambda_2\omega,v}}
T^=Tu^+Tv^V^=Vλ1ω^+Vλ2ω^H^=Hλ1ω,u^+Hλ2ω,v^
因此,本征波函數為
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\psi(x,y)=\psi_{\lambda_1\omega,m}(u)\psi_{\lambda_2\omega,n}(v)=\psi_{\lambda_1\omega,m}(q_{11}x+q_{12}y)\psi_{\lambda_2\omega,n}(q_{21}x+q_{22}y)
ψ(x,y)=ψλ1ω,m(u)ψλ2ω,n(v)=ψλ1ω,m(q11x+q12y)ψλ2ω,n(q21x+q22y)
對應的本征能級為
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E_{m,n}=\left[(m+\frac{1}{2})\lambda_1+(n+\frac{1}{2})\lambda_2\right]\hbar\omega=\left(\begin{matrix}m+\frac{1}{2}&n+\frac{1}{2}\end{matrix}\right)\sqrt{\Lambda}\left(\begin{matrix}1\\1\end{matrix}\right)\hbar\omega
Em,n=[(m+21)λ1+(n+21)λ2]ℏω=(m+21n+21)Λ(11)ℏω
5 正定勢場的定義
定義﹕ 對於任意向量 r ⃗ = ( x 1 , x 2 , ⋯ , x n ) T ≠ 0 ⃗ T \vec{r}=(x_1,x_2,\cdots,x_n)^T\neq\vec{0}^T r=(x1,x2,⋯,xn)T=0T,勢場
V ( r ⃗ ) = 1 2 m ω 2 r ⃗ T A r ⃗ > 0 V(\vec{r})=\frac{1}{2}m\omega^2\vec{r}^TA\vec{r}>0 V(r)=21mω2rTAr>0
其中 A A A 是一個實數矩陣,那麼勢場 V V V 就是正定勢場。
一般而言, A A A 會被寫成實對稱矩陣 (若非,則 A A A 可用 A + A T 2 \frac{A+A^T}{2} 2A+AT 代替),下一節的矩陣 A A A 都會默認是實對稱矩陣。根據線性代數知識可知, A A A 就是正定矩陣。
6 n n n 維「正定勢場」下的定態 Schrödinger 方程
試着把二維情況推廣到
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n 維空間中,結論又是否會成立呢?
考慮
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\vec{r}=(x_1,x_2,\cdots,x_n)^T\neq\vec{0}^T\\[1em] V(\vec{r})=\frac{1}{2}m\omega^2\vec{r}^TA_n\vec{r}
r=(x1,x2,⋯,xn)T=0TV(r)=21mω2rTAnr
V
V
V 是一個正定勢場,尋找其本征波函數
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\psi(\vec{r})
ψ(r)。
首先,對
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An 進行正交對角化,同時改寫勢能表達式﹕
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A_n = Q^T\Lambda Q\\ \Lambda=diag(\lambda_1^2,\lambda_2^2,\cdots,\lambda_n^2)\\[1em] Q=(q_{ij})_{n\times n}=\left(\begin{matrix}\vec{q_1}^T\\\vec{q_2}^T\\\vdots\\\vec{q_n}^T\end{matrix}\right)\\[1em] V = \frac{1}{2}m\omega^2\vec{r}^TQ^T\Lambda Q\vec{r}=\frac{1}{2}m\omega^2\vec{u}^T\Lambda\vec{u}=\sum_{i=1}^n\frac{1}{2}m(\lambda_i \omega)^2u_i^2\\(u_1,u_2,\cdots,u_n)^T=\vec{u}=Q\vec{r}
An=QTΛQΛ=diag(λ12,λ22,⋯,λn2)Q=(qij)n×n=⎝⎜⎜⎜⎛q1Tq2T⋮qnT⎠⎟⎟⎟⎞V=21mω2rTQTΛQr=21mω2uTΛu=i=1∑n21m(λiω)2ui2(u1,u2,⋯,un)T=u=Qr
然後,我們證明一個結論﹕
若存在一個正交矩陣 Q = { q i j } n × n Q=\{q_{ij}\}_{n\times n} Q={qij}n×n,滿足 u ⃗ = Q r ⃗ = ( q 1 ⃗ T q 2 ⃗ T ⋮ q n ⃗ T ) r ⃗ \vec{u}=Q\vec{r}=\left(\begin{matrix}\vec{q_1}^T\\\vec{q_2}^T\\\vdots\\\vec{q_n}^T\end{matrix}\right)\vec{r} u=Qr=⎝⎜⎜⎜⎛q1Tq2T⋮qnT⎠⎟⎟⎟⎞r,那麼
∇ r ⃗ 2 = ∇ u ⃗ 2 ( ∑ i = 1 n ∂ 2 ∂ x i 2 = ∑ i = 1 n ∂ 2 ∂ u i 2 ) \nabla^2_{\vec{r}}=\nabla^2_{\vec{u}}\ (\sum_{i=1}^n\frac{\partial^2}{\partial x_i^2}=\sum_{i=1}^n\frac{\partial^2}{\partial u_i^2}) ∇r2=∇u2 (i=1∑n∂xi2∂2=i=1∑n∂ui2∂2)
證﹕
∂ ∂ x i = ∑ k = 1 n ∂ ∂ u k ∂ u k ∂ x i = ∑ k = 1 n q k i ∂ ∂ u k ∂ 2 ∂ x i 2 = ( ∑ k = 1 n q k i ∂ ∂ u k ) ( ∑ m = 1 n q m i ∂ ∂ u m ) = ∑ k = 1 n ∑ m = 1 n q k i q m i ∂ 2 ∂ u k ∂ u m ∇ r ⃗ 2 = ∑ i = 1 n ∂ 2 ∂ x i 2 = ∑ i = 1 n ∑ k = 1 n ∑ m = 1 n q k i q m i ∂ 2 ∂ u k ∂ u m = ∑ k = 1 n ∑ m = 1 n [ ∂ 2 ∂ u k ∂ u m ( ∑ i = 1 n q k i q m i ) ] = ∑ k = 1 n ∑ m = 1 n [ ∂ 2 ∂ u k ∂ u m ( q k ⃗ T q m ⃗ ) ] = ∑ k = 1 n ∑ m = 1 n [ ∂ 2 ∂ u k ∂ u m δ k m ] = ∑ k = 1 n ∂ 2 ∂ u k 2 = ∇ u ⃗ 2 \frac{\partial}{\partial x_i}=\sum_{k=1}^n\frac{\partial}{\partial u_k}\frac{\partial u_k}{\partial x_i}=\sum_{k=1}^nq_{ki}\frac{\partial}{\partial u_k}\\[1em] \frac{\partial^2}{\partial x_i^2} = (\sum_{k=1}^nq_{ki}\frac{\partial}{\partial u_k})(\sum_{m=1}^nq_{mi}\frac{\partial}{\partial u_m})=\sum_{k=1}^n\sum_{m=1}^nq_{ki}q_{mi}\frac{\partial^2}{\partial u_k\partial u_m}\\[1em] \nabla^2_{\vec{r}}=\sum_{i=1}^n\frac{\partial^2}{\partial x_i^2}=\sum_{i=1}^n\sum_{k=1}^n\sum_{m=1}^nq_{ki}q_{mi}\frac{\partial^2}{\partial u_k\partial u_m}=\sum_{k=1}^n\sum_{m=1}^n\left[\frac{\partial^2}{\partial u_k\partial u_m}\left(\sum_{i=1}^nq_{ki}q_{mi}\right)\right]=\sum_{k=1}^n\sum_{m=1}^n\left[\frac{\partial^2}{\partial u_k\partial u_m}\left(\vec{q_k}^T\vec{q_m}\right)\right]=\sum_{k=1}^n\sum_{m=1}^n\left[\frac{\partial^2}{\partial u_k\partial u_m}\delta_{km}\right]=\sum_{k=1}^n\frac{\partial^2}{\partial u_k^2}=\nabla^2_{\vec{u}}\\[1em] ∂xi∂=k=1∑n∂uk∂∂xi∂uk=k=1∑nqki∂uk∂∂xi2∂2=(k=1∑nqki∂uk∂)(m=1∑nqmi∂um∂)=k=1∑nm=1∑nqkiqmi∂uk∂um∂2∇r2=i=1∑n∂xi2∂2=i=1∑nk=1∑nm=1∑nqkiqmi∂uk∂um∂2=k=1∑nm=1∑n[∂uk∂um∂2(i=1∑nqkiqmi)]=k=1∑nm=1∑n[∂uk∂um∂2(qkTqm)]=k=1∑nm=1∑n[∂uk∂um∂2δkm]=k=1∑n∂uk2∂2=∇u2
因此,對應的算符量是
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\hat{T_i}=-\frac{\hbar^2}{2m}\frac{\partial^2}{\partial u_i^2}\\[1em] \hat{V_{\lambda_i\omega,i}}=\frac{1}{2}m(\lambda_i \omega)^2u_i^2\\[1em] \hat{H_{\lambda_i\omega,i}}=\hat{T_i}+\hat{V_{\lambda\omega,i}}\\[1em] \hat{H}=\sum_{i=1}^n\hat{H_{\lambda_i\omega,i}}
Ti^=−2mℏ2∂ui2∂2Vλiω,i^=21m(λiω)2ui2Hλiω,i^=Ti^+Vλω,i^H^=i=1∑nHλiω,i^
如第 3 節的「
n
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n 維諧振子」般利用數學歸納法可得,本征波函數
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\psi(\vec{r})=\prod_{i=1}^{n}\psi_{\lambda_i\omega,m_i}(\vec{q_i}^T \vec{r})
ψ(r)=i=1∏nψλiω,mi(qiTr)
對應的本征能級
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\vec{m}=(m_i)^T_{n\times 1}
m=(mi)n×1T 是
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E_{\vec{m}}=\hbar\omega\sum_{i=1}^n(m_i+\frac{1}{2})\lambda_i=(\vec{m}^T+(\frac{1}{2})_{1\times n})\sqrt{\Lambda}(1)_{n\times 1}\hbar\omega
Em=ℏωi=1∑n(mi+21)λi=(mT+(21)1×n)Λ(1)n×1ℏω
7 資料來源
《量子力學》,錢伯初,高等教育出版社,2017年。 ↩︎
一維諧振子https://en.wikipedia.org/wiki/Schr%C3%B6dinger_equation#Harmonic_oscillator ↩︎
Gilbert Strang, Introduction to Linear Algebra, fifth edition ↩︎