# Quantum Theory of the hydrogen Atom And Many-Electron Atoms

General outline
• Schrödinger Equation in Spherical coordinates • The hydrogen atom wave function • Radial probability densities • Angular momentum • Intrinsic spin • Energy levels • The Zeeman effect

The Quantum Model of the Hydrogen Atom
• The potential energy function for the hydrogen atom is
e2 U (r ) = − k e r
– ke is the Coulomb constant – r is the radial distance from the proton to the electron
• The proton is situated at r = 0

• The formal procedure to solve the hydrogen atom is to substitute U(r) into the Schrödinger equation and find the appropriate solutions to the equations • Because it is a three-dimensional problem, it is easier to solve if the rectangular coordinates are converted to spherical polar coordinates
h 2  ∂ 2ψ ∂ 2ψ ∂ 2ψ   2 + 2 + 2  + Uψ = Eψ − 2m  ∂x ∂z  ∂y  

• ψ(x, y, z) is converted to ψ(r, θ, φ) • Then, the space variables can be separated: ψ(r, θ, φ) = R(r), ƒ(θ), g(φ) • When the full set of boundary conditions are applied, we are led to three different quantum numbers for each allowed state

Wave function of the electron in a hydrogen atom (in spherical polar coordinate)

∂ψ  ∂ ψ ∂  ∂  2 ∂ψ  sin θ  r + 2  + sin θ  sin θ ∂θ  ∂φ ∂θ  ∂r  ∂r 
2 2

  e2 2mr sin θ  + E ψ = 0 + 2   4πε r h o  
2 2

Quantum Numbers, General
• The three different quantum numbers are restricted to integer values • They correspond to three degrees of freedom
– Three space dimensions

Principal Quantum Number
• The first quantum number is associated with the radial function R(r)
– It is called the principal quantum number – It is symbolized by n

• The potential energy function depends only on the radial coordinate r • The energies of the allowed states in the hydrogen atom are the same En values found from the Bohr theory

Orbital and Orbital Magnetic Quantum Numbers
• The orbital quantum number is symbolized by ℓ
– It is associated with the orbital angular momentum of the electron – It is an integer

• The orbital magnetic quantum number is symbolized by mℓ
– It is also associated with the angular orbital momentum of the electron and is an integer

Quantum Numbers - Summary of Allowed Values
• • • • The values of n can range from 1 to ∞ The values of ℓ can range from 0 to n - 1 The values of mℓ can range from –ℓ to ℓ Example:
– If n = 1, then only ℓ = 0 and mℓ = 0 are permitted – If n = 2, then ℓ = 0 or 1
• If ℓ = 0 then mℓ = 0 • If ℓ = 1 then mℓ may be –1, 0, or 1

Quantum Numbers, Summary Table

Shells
• Historically, all states having the same principle quantum number are said to form a shell
– Shells are identified by letters K, L, M,…

• All states having the same values of n and ℓ are said to form a subshell
– The letters s, p, d, f, g, h, .. are used to designate the subshells for which ℓ = 0, 1, 2, 3,…

Shell and Subshell Notation, Summary Table

Wave Functions for Hydrogen
• The simplest wave function for hydrogen is the one that describes the 1s state and is designated ψ1s(r) 1 ψ1s (r ) = e −r ao 3 πao • As ψ1s(r) approaches zero, r approaches ∞ and is normalized as presented • ψ1s(r) is also spherically symmetric
– This symmetry exists for all s states

Probability Density
• The probability density for the 1s state is

 1  −2r ao ψ1s =  3  e  πao  • The radial probability density function P(r) is the probability per unit radial length of finding the electron in a spherical shell of radius r and thickness dr
2

Radial Probability Density
• A spherical shell of radius r and thickness dr has a volume of 4πr2 dr • The radial probability function is P(r) = 4πr2 |ψ|2

P(r) for 1s State of Hydrogen
• The radial probability density function for the hydrogen atom in its ground state is
 4r 2  −2r ao P1s (r ) =  3  e  ao 

• The peak indicates the most probable location • The peak occurs at the Bohr radius

P(r) for 1s State of Hydrogen
• The average value of r for the ground state of hydrogen is 3/2 ao
– The graph shows asymmetry, with much more area to the right of the peak

• According to quantum mechanics, the atom has no sharply defined boundary as suggested by the Bohr theory

Electron Clouds
• The charge of the electron is extended throughout a diffuse region of space, commonly called an electron cloud • This shows the probability density as a function of position in the xy plane • The darkest area, r = ao, corresponds to the most probable region

Wave Function of the 2s state
• The next-simplest wave function for the hydrogen atom is for the 2s state
– n = 2; ℓ = 0

• The wave function is
1 ψ2 s (r ) = 4 2π  1  2 r  −r 2ao    2 − e ao   ao  
3

– ψ 2s depends only on r and is spherically symmetric

Comparison of 1s and 2s States
• The plot of the radial probability density for the 2s state has two peaks • The highest value of P corresponds to the most probable value
– In this case, r ≈ 5ao

Physical Interpretation of ℓ
• The magnitude of the angular momentum of an electron moving in a circle of radius r is L = mevr • The direction of L is perpendicular to the plane of the circle • In the Bohr model, the angular momentum of the electron is restricted to multiples of h

• According to quantum mechanics, an atom in a state whose principle quantum number is n can take on the following discrete values of the magnitude of the orbital angular momentum:
L = l( l + 1 )h l = 0 ,1,2...n − 1

– L can equal zero, which causes great difficulty when attempting to apply classical mechanics to this system

Physical Interpretation of mℓ
• The atom possesses an orbital angular momentum • There is a sense of rotation of the electron around the nucleus, so that a magnetic moment is present due to this angular momentum • There are distinct directions allowed for the magnetic moment vector with respect to the magnetic field vector B

• Because the magnetic moment of the atom can be related to the angular momentum vector, L, the discrete direction of translates into the fact that the direction of L is quantized • Therefore, Lz, the projection of L along the z axis, can have only discrete values

• The orbital magnetic quantum number mℓ specifies the allowed values of the z component of orbital angular momentum • Lz = mℓ ħ • The quantization of the possible orientations of L with respect to an external magnetic field is often referred to as space quantization

• L does not point in a specific direction – Even though its z-component is fixed – Knowing all the components is inconsistent with the uncertainty principle • Imagine that L must lie anywhere on the surface of a cone that makes an angle θ with the z axis • L can never be aligned parallel or antiparallel to B because Lz must be less than the total angular momentum, L. • For Lz to be zero, L must be perpendicular to B

• θ is also quantized • Its values are specified through Lz ml = cos θ = L l ( l + 1) • mℓ is never greater than ℓ, therefore θ can never be zero

Zeeman Effect
• The Zeeman effect is the splitting of spectral lines in a strong magnetic field • In this case the upper level, with ℓ = 1, splits into three different levels corresponding to the three different directions of

• The torque, τ, on a magnetic dipole in the presence of external magnetic field, B:
τ = µB sin θ potential energy : U = ∫ τdθ = −µB cos θ
π/ 2 θ

θ B

 e  µ = − L  2m  e U= LB cos θ 2m ml cos θ = l (l + 1)

 eh  U = ml  B  2m 

• µB = eħ/2m = Bohr magneton = 9.274 x 10-24 J/T

Spin Quantum Number ms
• Electron spin does not come from the Schrödinger equation • Additional quantum states can be explained by requiring a fourth quantum number for each state • This fourth quantum number is the spin magnetic quantum number ms

• Unusual feature was observed in the spectra of certain gases, such as sodium vapor • Close examination shows that one prominent line in the spectra is actually consist of 2 closely spaced lines (doublet) – Fine Structure • A need for a new quantum number!

Stern–Gerlach experiment

• If the particle travels through an inhomogeneous magnetic field, then the force on one end of the dipole will be slightly greater than the opposing force on the other end of the dipole. • This leads to the particle being deflected in the inhomogeneous magnetic field. The direction in which the particles are deflected is typically called the "z" direction.

• If the particles are classical, "spinning" particles, then the distribution of their spin angular momentum vectors is taken to be truly random and each particle would be deflected up or down by a different amount, producing an even distribution on the screen of a detector. • Instead, the particles passing through the device are deflected either up or down by a specific amount. This can only mean that spin angular momentum is quantized, i.e. it can only take on discrete values. There is not a continuous distribution of possible angular momenta.

Electron Spins
• Only two directions exist for electron spins • The electron can have spin up (a) or spin down (b) • In the presence of a magnetic field, the energy of the electron is slightly different for the two spin directions and this produces doublets in spectra of certain gases

• The concept of a spinning electron is conceptually useful • The electron is a point particle, without any spatial extent
– Therefore the electron cannot be considered to be actually spinning

• The experimental evidence supports the electron having some intrinsic angular momentum that can be described by ms • Dirac showed this results from the relativistic properties of the electron

Spin Angular Momentum
• The total angular momentum of a particular electron state contains both an orbital contribution L and a spin contribution S • Electron spin can be described by a single quantum number s, whose value can only be s = ½ • The spin angular momentum of the electron never changes

• The magnitude of the spin angular momentum is
3 S = s(s + 1)h = h 2

• The spin angular momentum can have two orientations relative to a z axis, specified by the spin quantum number ms = ± ½
– ms = + ½ corresponds to the spin up case – ms = - ½ corresponds to the spin down case

• The z component of spin angular momentum is Sz = ms ħ = ± ½ ħ • Spin angular moment S is quantized

Spin Magnetic Moment
• The spin magnetic moment spin is related to the spin angular momentum by
µspin e =− S me

• The z component of the spin magnetic moment can have values
µspin , z eh =± 2me

The Exclusion Principle
• The four quantum numbers discussed so far can be used to describe all the electronic states of an atom regardless of the number of electrons in its structure • How many electron can be in a particular quantum state? • The exclusion principle states that no two electrons can ever be in the same quantum state
– Therefore, no two electrons in the same atom can have the same set of quantum numbers

Filling Subshells
• Once a subshell is filled, the next electron goes into the lowest-energy vacant state
– If the atom were not in the lowest-energy state available to it, it would radiate energy until it reached this state

Orbitals
• An orbital is defined as the atomic state characterized by the quantum numbers n, ℓ and mℓ • From the exclusion principle, it can be seen that only two electrons can be present in any orbital
– One electron will have spin up and one spin down

Allowed Quantum States, Example

• In general, each shell can accommodate up to 2n2 electrons

Hund’s Rule
• Hund’s Rule states that when an atom has orbitals of equal energy, the order in which they are filled by electrons is such that a maximum number of electrons have unpaired spins
– Some exceptions to the rule occur in elements having subshells that are close to being filled or half-filled

Periodic Table
• The chemical behavior of an element depends on the outermost shell that contains electrons • For example, the inert gases (last column) have filled subshells and a wide energy gap occurs between the filled shell and the next available shell

Hydrogen Energy Level Diagram Revisited
• The allowed values of ℓ are separated • Transitions in which ℓ does not change are very unlikely to occur and are called forbidden transitions
– Such transitions actually can occur, but their probability is very low compared to allowed transitions

Selection Rules
• The selection rules for allowed transitions are
– ∆ℓ = ±1 – ∆mℓ = 0, ±1

• The angular momentum of the atom-photon system must be conserved • Therefore, the photon involved in the process must carry angular momentum
– The photon has angular momentum equivalent to that of a particle with spin 1 – A photon has energy, linear momentum and angular momentum

Multielectron Atoms
• For multielectron atoms, the positive nuclear charge Ze is largely shielded by the negative charge of the inner shell electrons
– The outer electrons interact with a net charge that is smaller than the nuclear charge

• Allowed energies are
2 13.6 Zeff En = − eV 2 n
2 Z eff = effective atomic number