Variational Principle on First Excited State

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SUMMARY

The discussion centers on proving the variational principle for the first excited state in quantum mechanics. The principle states that if the overlap between the trial wave function and the ground state wave function is zero, then the expectation value of the Hamiltonian, , is greater than or equal to the energy of the first excited state, E_{fe}. The proof involves expressing the trial wave function as a linear combination of states excluding the ground state and demonstrating that the coefficients satisfy the normalization condition, leading to the conclusion that ≥ E_{fe} when c_{1} = 0.

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  • Understanding of quantum mechanics, specifically the variational principle.
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Students and researchers in quantum mechanics, physicists focusing on quantum theory, and anyone interested in understanding the variational principle and its implications for excited states in quantum systems.

boyu
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I am trying to prove the variational principle on 1st excited state, but have some questions here.

The theory states like this: If <\psi|\psi_{gs}>=0, then <H>\geq E_{fe}, where 'gs' stands for 'grand state' and 'fe' for 'first excited state'.

Proof: Let ground state denoted by 1, and first excited state denoted by 2, i.e., |\psi_{1}>=|\psi_{gs}>, |\psi_{2}>=|\psi_{fe}>


<\psi|\psi_{1}>=0 ---> |\psi>=\sum^{\infty}_{n=2}c_{n}\psi_{n}

<H>=<\psi|H\psi>=<\sum^{\infty}_{m=2}c_{m}\psi_{m}|E_{n}\sum^{\infty}_{n=2}c_{n}\psi_{n}>=\sum^{\infty}_{m=2}\sum^{\infty}_{n=2}E_{n}c^{*}_{m}c_{n}<\psi_{m}|\psi_{n}>=\sum^{\infty}_{n=2}E_{n}|c_{n}|^{2}

Since n\geq 2, E_{n}\geq E_{2}=E_{fe}


so <H>\geq \sum^{\infty}_{n=2}E_{fe}|c_{n}|^{2}=E_{fe}\sum^{\infty}_{n=2}|c_{n}|^{2}


Then how to get the conclusion of <H>\geq E_{fe}, since \sum^{\infty}_{n=2}|c_{n}|^{2}=1-|c_{1}|^{2}\leq 1?

Edit: I've got the answer. c_{1}=0. Thx.
 
Last edited:
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Correct. One has
$$
\sum_{n=2}^{\infty} |c_n|^2 = 1
$$
 

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