What do the subscripts in the wave function psi_(nlm_l)(r,theta,phi)ψnlml(r,θ,ϕ) indicate?

1 Answer
Sep 16, 2017

They specify what orbitals the wave functions describe. They are the quantum numbers.


The wave function psi_(nlm_l)(r,theta,phi) = R_(nl)(r)Y_(l)^(m_l)(theta,phi)ψnlml(r,θ,ϕ)=Rnl(r)Ymll(θ,ϕ) for the hydrogen atom describes the state of its atomic orbitals, and require the use of quantum numbers to describe which one we refer to.

So if we wish to specify a 2p2p orbital, we pick the wave function with n = 2n=2, l = 1l=1, and some m_lml in the set {-1,0,+1}{1,0,+1}. We then know that we refer to:

psi_(21-1)(r,theta,phi) = R_(21)(r)Y_(1)^(-1)(theta,phi) = psi_(2px)ψ211(r,θ,ϕ)=R21(r)Y11(θ,ϕ)=ψ2px

psi_(211)(r,theta,phi) = R_(21)(r)Y_(1)^(1)(theta,phi) = psi_(2py)ψ211(r,θ,ϕ)=R21(r)Y11(θ,ϕ)=ψ2py

psi_(210)(r,theta,phi) = R_(21)(r)Y_(1)^(0)(theta,phi) = psi_(2pz)ψ210(r,θ,ϕ)=R21(r)Y01(θ,ϕ)=ψ2pz

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And these would be given by one radial component (specifying that we refer to 2p2p orbitals):

R_(21)(r) = 1/(2sqrt6)(Z/a_0)^(3//2)sigmae^(-sigma//2)R21(r)=126(Za0)3/2σeσ/2

where sigma = Zr//a_0σ=Zr/a0 (a_0 = "0.529177 pm"a0=0.529177 pm being the Bohr radius and ZZ being the atomic number),

and three different angular components (specifying which particular 2p2p orbitals we refer to):

Y_(1)^(-1)(theta,phi) = 1/(2sqrt2) sqrt(3/pi) sintheta e^(-iphi)Y11(θ,ϕ)=1223πsinθeiϕ

Y_(1)^(1)(theta,phi) = 1/(2sqrt2) sqrt(3/pi) sintheta e^(iphi)Y11(θ,ϕ)=1223πsinθeiϕ

Y_(1)^(0)(theta,phi) = 1/2 sqrt(3/pi)costhetaY01(θ,ϕ)=123πcosθ

And in fact, these three Y_(l)^(m_l)(theta,phi)Ymll(θ,ϕ) can be used represent any hydrogen-like pp orbital, not just the 2p2p, as they do not depend on the principal quantum number nn.