Upper bound for first excited state - variational principle

AI Thread Summary
The discussion focuses on solving a quantum mechanics problem related to the upper bound for the first excited state using the variational principle. The user derived expressions for the upper bound energy and found a candidate wavefunction, resulting in an upper bound of 2.423 for the first excited state, while the actual energy calculated using the shooting method was 4.696. The user confirmed the accuracy of their method for the ground state, where the upper bound of 0.68142 was consistent with the exact energy of 0.667986. A key question raised was about the boundary conditions for the first excited state wavefunction, specifically whether the derivative at zero should equal zero. The discussion highlights the importance of correctly applying boundary conditions in variational methods.
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Homework Statement
Find the upper bound of the first excited energy eigenstate in the quartic potential using variational principle.
Relevant Equations
Time-independent Schrodinger equation:
$$
-\frac{\hbar}{2m}\frac{\partial^2 \psi}{\partial x^2}+\alpha x^{4} \psi=E \psi
$$
Dimensionless time-independent Schrodinger equation
$$
-\frac{1}{2}\frac{\partial^2 \psi}{\partial u^2}+(u^{4} - e) \psi=0
$$
Variational principle:
$$
E_{1}\leqslant \int_{-\infty }^{\infty }\psi^{*}(x)H\psi(x)dx
$$
I'm solving problem number 5 from https://ocw.mit.edu/courses/8-05-quantum-physics-ii-fall-2013/resources/mit8_05f13_ps2/.

(a) Here I got:
$$
\beta = \frac{\hbar^{\frac{1}{3}}}{(\alpha m)^\frac{1}{6}}
$$
and:
$$
E = \left ( \frac{\alpha \hbar^4}{m^2} \right )^\frac{1}{3}e
$$
(b) Using Scilab I found that for the ground state energy:
$$
e_{0}=0.667986
$$
(c) A candidate wavefunction for the variational principle is:
$$
\psi _{1}=Axe^{-\frac{ax^2}{2}}
$$
(It is chosen to be orthogonal to ##\psi _{0}##.)
Here I got that upper bound for the first excited state is:
$$
h_{1}=\frac{3}{4}\left ( 10^{\frac{1}{3}} + \frac{5}{100^{\frac{1}{3}}} \right )=2.423
$$
(d) But here, by using shooting method, I got that:
$$
e_{1}=4.696
$$
or, the upper bound is less than the actual energy of the first excited state.
I'm not sure what went wrong.

I have to mention that I checked this for the ground state energy. By using the trial wave function:
$$
\psi _{0}=Be^{-\frac{ax^2}{2}}
$$
I got the upper bound for the ground state energy:
$$
h_{0}=\frac{1}{4}\left ( 6^{\frac{1}{3}} + \frac{3}{36^{\frac{1}{3}}} \right )=0.68142
$$
and exact ground state energy obtained by using the shooting method is:
$$
e_{1}=0.667986
$$
which is OK: exact value of the ground state energy is little bellow the upper bound.
The Scilab source follows:
```
//Solve a second order differential equation
//Y’’= 2(x^4-e)y, y(0)=1 and y’(0)=0
//e0=0.6679863 - dimensionless gruound state energy
funcprot(0)

function dy=f(x, y)
dy(1)=y(2);
dy(2)=2*(x^4-0.6679863)*y(1);
endfunction

x0=0;
xmax=10;
x=x0:0.1:xmax;
y0=1;
dy0=0;

y=ode([y0;dy0],x0,x,f);

clf;

plot(x,y(1,:),"r")
plot(x,y(2,:),"g")

xtitle("$\frac{d^2 y}{dx^2} =2*(x^4-0.6679863)*y $","x","f(x,y)");

legend("x","dy/dx")
 
Last edited:
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What is ##\psi(0)## for the first excited state?
Does ##\psi'(0) = 0## for the first excited state?
 
Last edited:
Oh!
I did't think of that at all. Thank you!
 
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