QM.4 · Finite-well bound states and hydrogenic quantum numbers

Declare a symmetric well V=−V₀ for |x|<a and V=0 outside, with V₀>0 and the same mass throughout. A bound energy lies between −V₀ and zero. Inside, k=√[2m(E+V₀)]/$\hbar$ gives oscillatory solutions; outside, κ=√(−2mE)/$\hbar$ gives decaying tails. Reject growing exponentials to obtain a normalisable state. Reflection symmetry permits even interior cos(kx) or odd sin(kx) states. At finite boundaries without delta interactions, both ψ and ψ′ are continuous. Even matching gives k tan(ka)=κ; odd matching gives −k cot(ka)=κ. A finite well does not require ψ to vanish at its edges as an infinite wall does.

Introduce z=ka and ρ=a√(2mV₀)/$\hbar$. Then κa=√(ρ²−z²) and 0<z<ρ. Solve z tan z=√(ρ²−z²) for an even state, or −z cot z=√(ρ²−z²) for an odd one, on intervals with the appropriate sign and away from tangent poles. Energy follows as E/V₀=z²/ρ²−1. For ρ=1, the ground root lies in 0<z<1 and the even equation is equivalent there to z=cos z. Bisection or a converged root finder gives z≈0.739085 and E/V₀≈−0.453753. Since ρ<π/2, no odd bound-state branch fits. In one dimension an attractive square well has an even bound ground state however shallow it is; an E=0 threshold tail is not square integrable.

For a one-electron Coulomb ion with nuclear charge Ze, use the nonrelativistic central-potential model and a heavy nucleus approximation unless reduced mass is specified. E_n≈−13.6 Z²/n² eV; allowed orbital numbers are n≥1, l=0,…,n−1 and m_l=−l,…,l. L² has eigenvalue l(l+1)$\hbar$² and L_z=m_l$\hbar$; the ground 1s orbital has l=0, despite the historical Bohr circular-orbit rule. Spatial degeneracy at fixed n is Σ_l(2l+1)=n² before spin and fine-structure corrections. If ψ=R_nl(r)Y_lm with angular part normalised, radial probability in dr is r²|R|²dr, not just |R|²dr. For hydrogen 1s, the radial density is 4r²e^(−2r/a₀)/a₀³: it peaks at r=a₀ and has mean 3a₀/2, while the three-dimensional point density is largest at the origin. Distinguish these measures before locating a most probable radius.

A finite well has V = -V0 for $|x| and zero outside. A bound energy lies strictly between -V0 and zero. Define

Even parity gives an interior cosine and decaying tails. Matching value and derivative at a gives Odd parity instead gives $-k\cot(ka)=\kappa$. Solve only within valid parity intervals; a root at a tangent pole is not a bound state.