Quantum Mechanics for Chemical Engineers Lecture 12

Atomic Structure and Spectra:

Hydrogenic Atom

Byungchan Han
Department of Chemical & Biomolecular Engineering,Yonsei University
April 12, 2016 (Tuesday)
 Hydrogenic Atom
Electronic Structure of an Atom: electron configurations around its nucleus
• Determines Structure and Reactivity of Atoms and Molecules
Hydrogenic atom: a one-electron atom or ion of general atomic number Z
• H, He+, Li2+, O7+, U91+, …
Many-electron atom (poly-electronic atom)
• All neutral atoms other than H including He.

Electric discharge is passed through gaseous hydrogen

• The H2 molecules are dissociated into H atoms.
• The energetically excited H atoms emit light of discrete frequencies.
• The spectrum consists of a series of ‘lines’.
 Atomic Structure and Spectra:
Hydrogenic Atom
Spectral Lines of a H Johannes Rydberg

1 ⎛ 1 1⎞
= ν = RH ⎜ 2 − 2 ⎟ , ν = c × ν!
!
λ ⎝ n1 n2 ⎠
me e 4
RH = 2 3
8ε o h c
= 1.0973731568539(55) × 10 7 m −1
⎧n1 = 1 : Lyman
⎪
⎨n1 = 2 : Balmer
⎪n = 3 : Paschen
⎩ 1
n2 = n1 + 1,n1 + 2,n1 + 3,...

The shortest and longest wavelength lines in the Balmer series?

R! H Wavenumber of any spectral line (of any atom, not just hydrogenic atoms) is the difference
Tn = 2 ; between two terms,
n
ν! = T1 − T2 ; Ritz Combination Principle
 Origin of the Energy Quantization,
Permitted Energy Levels
Ze2
V= !
4πε 0 r N −e • Central Potential: Potential depends only on the distance (r) from the nucleus

Ĥ = ÊKE,e + ÊKE,N + ÊPE (= V̂ ) Decouple Motions and Separation of Variables (due to V)

!2 2 !2 2 Ze2 1.Motion of the Atom as a whole through space.
=− ∇e − ∇N − ! 2.Motion of the Electron relative to the nucleus.
2me 2mN 4πε 0 r N −e

!2 2 Ze2
− ∇ψ − ψ = Eψ : SDE for a Hydrogenic Atom
2µ 4πε 0 r
1 1 1 • Motion of the electron relative to the nucleus
= + • Internal motion of the electron relative to the nucleus
µ me m N
µ ! Reduced Mass ≈ me (∵ me ≪ mN )
Adiabatic Approximation (Born-Oppenheimer Approximation)
 SDE for Hydrogenic Atoms
!2 2 Ze2
− ∇ψ − ψ = Eψ
2µ 4πε 0 r

Separation of Variables: Radial Wavefunction & Angular Wavefunction

× r2/RY for the both sides

Should Constant. why?

= SDE for a Particle on a Sphere.

 Radial Wavefunctions

⎡ !2 d 2 ⎤ Ze2 l(l + 1)! 2

⎢ − 2 µ dr 2 + Veff ⎥ u = Eu : u = Rr, Veff = − 4πε r1 + 2 µr 2
⎣ ⎦ 0

⎧ Ze2
⎪ 4πε r1 :Coulomb potential energy of the electron in the field of the nucleus.
⎪ 0
Veff ⎨
⎪ l(l + 1)! :Centrifugal force that arises from the angular momentum of the electron around the nucleus
2

⎪⎩ 2 µr 2

• Close to the nucleus the radial wavefunction is proportional to rl.

• The higher the orbital angular momentum the less probability to find the electron there.
• Far from the nucleus all radial wavefunctions approach zero exponentially.
 ⎡ !2 d 2 ⎤ Ze2 l(l + 1)! 2
⎢ − 2 µ dr 2 + Veff ⎥ u = Eu : u = Rr, Veff = − 4πε r1 + 2 µr 2
⎣ ⎦ 0

neglect
As r → 0 ⎡ !2 d 2 Ze2 l(l + 1)! 2 ⎤
u = Rr ≈ 0 ⎢ − 2 µ dr 2 − 4πε r1 + 2 µr 2 ⎥ u = Eu =0
⎣ 0 ⎦

⎡ d 2 l(l + 1) ⎤ B
⎢ − dr 2 + r 2 ⎥ u = 0 → u(r) = Ar + r l
l+1

⎣ ⎦
• At r =0, B should be zero. Why?
• R (= u/r) cannot be infinite anywhere and specifically at r = 0, B = 0.
• So, R (r → 0) ≈ Arl

Far from r = 0 (the nucleus)

!2 d 2 R
⎡ !2 d 2 Ze2
neglect neglect
l(l + 1)! 2 ⎤ − = ER
⎢ − 2 µ dr 2 − 4πε r1 + 2 µr 2 ⎥ u = Eu 2 µ dr 2

⎣ 0 ⎦
2µ E
− r

d 2u d 2 ( rR ) d ⎛ d ( rR ) ⎞ d2R dR d2R R=e !2

= = ⎜ ⎟ =r 2 +2 ≈r 2
dr 2
dr 2
dr ⎝ dr ⎠ dr dr dr
 • Close to the nucleus, orbitals with l = 1 are proportional to r1, orbitals with
l = 2 are proportional to r2, and orbitals with l = 3 are proportional to r3.
• Electrons are progressively excluded from the neighborhood of the
nucleus as l increases. An orbital with l = 0 has a finite, nonzero value at
the nucleus.
• The form rl close to the nucleus blends into the exponentially decaying
form at great distances.

R(r) = r l × ( polynomial in r ) × ( decaying exponential in r )

dominant @r → 0 dominant @r → ∞
− ρ /2
Rn,l (r) = N n,l ρ l L2l+1
n+1 ( ρ )e
⎧ 2Zr 4πε 0 ! 2
⎪ρ = , a0 = 2
= Bohr ' s Radius = 52.9 pm
⎨ na0 me e
⎪ L2l+1 ( ρ ) : Associated Laguerre Polynomial
⎩ n+1

Z 2 µe4
En = − (n=1,2,3,...)
Edmond Nicolas Laguerre 32π ε 0 ! n
2 2 2 2

(1834 - 1886), France

 − ρ /2
Rn,l (r) = N n,l ρ l L2l+1
n+1 ( ρ )e
⎧ 2Zr 4πε 0 ! 2
⎪ρ = , a0 =
⎨ na0 me e 2
⎪ L2l+1 ( ρ ) : Associated Laguerre Polynomial
⎩ n+1

The exponential factor ensures that the wavefunction approaches zero far from the nucleus.
The factor ρl ensures that (provided l > 0) the wavefunction vanishes at the nucleus.
The associated Laguerre polynomial is a function that in general oscillates from positive to negative
values and accounts for the presence of radial nodes.
The radial wavefunctions of the first few states of hydrogenic atoms of atomic number Z.
Calculate the probability density at the nucleus for an electron with n = 1, l = 0, and ml = 0.

3/2
⎛Z⎞
1/2
⎛ 1 ⎞
ψ 1,0,0 ( r = 0,θ , φ ) = R1,0 (0)Y0,0 (θ , φ ) = 2 ⎜ ⎟ ⎜⎝ ⎟
⎝ a0 ⎠ 4π ⎠
Z3
ψ 1,0,0 ( r = 0,θ , φ )
2
= 3 = 2.15 × 10 −6 pm with Z = 1
π a0
 Atomic Orbitals and Their Energies
You already knew that ….
• Atomic Orbital: a one-electron wavefunction for an electron in an atom.
• Atomic orbitals are specified by the quantum numbers n, l, and ml.
• The energies of the bound states of hydrogenic atoms are proportional to Z2/n2.
• The ionization energy of an element is the minimum energy required to remove an electron
from the ground state of one of its atoms.
• Orbitals of a given value of n form a shell of an atom, and within that shell orbitals of the
same value of l form subshells.
• s Orbitals are spherically symmetrical and have nonzero probability density at the nucleus.
• A radial distribution function is the probability density for the distribution of the electron as a
function of distance from the nucleus.
• There are three p (l=1)orbitals in a given subshell; each one has an angular node.
• There are five d (l = 2)orbitals in a given subshell; each one has two angular nodes.

Electron described by the wavefunction ψ n,l,ml and in the state n,l, ml (Dirac Notation)
is said to occupy the orbital with n, l, ml .
 Specification of Orbitals
You already knew that ….
• Principal Quantum Number n (1, 2, 3, …): determines the energy of the electron.

Z 2 µe4
En = − (n=1,2,3,...)
32π ε 0 ! n
2 2 2 2

• Quantum numbers l, ml come from the angular solutions, and specify the angular momentum
of the electron around the nucleus
• Angular Momentum: l(l + 1)! ;l = 0,1,...,l − 1

• An electron in an orbital with quantum number ml has a z-component of angular momentum

ml ! ; ml = 0, ±1, ±2,..., ±l

n controls the maximum value of l.

l controls the range of values of ml.

⎧Orbital :l, ml
Total Wavefunction = (Orbital ) × ( Spin State ) ⎨
⎩ Spin : s ( = 1
2 ) , m s ( = ± 2 ) foran electron
1

To specify the state of an electron in a hydrogenic atom we need 4 quantum numbers : n,l, ml , ms
The single electron in a certain excited state of a hydrogenic He+ ion (Z = 2) is described by
the wavefunction R3,2(r)×Y2,−1 (θ, φ).
What are the energy, total angular momentum, and z-component of the angular momentum
of its electron?

n = 3, l = 2, ml = -1

Z 2 µe4
En = − (n=1,2,3,...) with µ ≈ m → E = −9.676 × 10 −19
J
32π ε 0 ! n
2 2 2 2 e 3

l = 2; Magnitude of Angular Momentum = l(l + 1)! → 6!

ml = −1 → Magnitude of Angular Momentum in z - component = −!
 Energy Levels
• ∆En ∝ Z2
• Bound states of the atom : All E < 0 (Quantized)
• Unbound states: E > 0 (Continuous—continuum states )

µ H e4
hcRH = = Ionization Energy for H = 13.60 eV
32π ε 0 !
2 2 2

where, RH is the Rydberg constant for H (Z=1), µ H is the reduced mass of H

µH
RH = R∞
me
me e 4
R∞ ! 2 3 ; Rydberg Constant
8ε 0 h c

Ionization Energy: the minimum energy required to remove an electron from the
ground state, the state of lowest energy, of one of its atoms in the gas phase.

Z 2 µe4 hcRH
En = − = − ; (n=1,2,3,...)
32π ε 0 ! n
2 2 2 2
n 2

Z 2 µe4
En = − (n=1,2,3,...)
32π ε 0 ! n
2 2 2 2
The emission spectrum of H atom shows lines at 82259, 97492, 102824, 105292, 106632, and
107440 cm−1, which correspond to transitions to the same lower state.
Determine (a) the ionization energy of the lower state, (b) the value of the Rydberg constant.

Z 2 µe4 hcRH
En = − = − ; (n=1,2,3,...)
32π ε 0 ! n
2 2 2 2
n 2

hc hcR hcR I R
ΔE = = hcν̂ = − 2 H − Elower = − 2 H + I → ν̂ = − H2
λ n n hc n

Slope: -RH
Intercept: I/hc
 Shells and Subshells

Energy Level

For a given principal quantum number n

• There are n subshells & n2 orbitals
• In a hydrogenic atom each energy level is n2-fold degenerate.
• Total 2n2 electrons can occupy the shell
 Shells and Subshells

Energy Level

For a given principal quantum number n

• There are n subshells & n2 orbitals
• In a hydrogenic atom each energy level is n2-fold degenerate.
• Total 2n2 electrons can occupy the shell
 s Orbitals

The balance of kinetic and potential energies that accounts

for the structure of the ground state of hydrogen (and
similar atoms).
(a) The sharply curved but localized orbital has high mean
kinetic energy, but low mean potential energy;
(b) the mean kinetic energy is low, but the potential energy
is not very favorable;
(c) the compromise of moderate kinetic energy and
moderately favorable potential energy.

Energies of ns orbitals increase (become less negative; the electron becomes less tightly bound) as n↑
because the average distance of the electron from the nucleus increases.
By the virial theorem with b = −1, <Ek> = −½ <V> so, even though the average kinetic energy decreases
as n↑, the total energy is equal to +½ <V>, which becomes less negative as n↑.

• The kinetic energy becomes less positive and has fallen to zero when n = ∞ .
• The potential energy becomes less negative and has risen to zero when n = ∞ .
• The total energy becomes less negative and and has risen to zero when n = ∞ .
 Use hydrogenic orbitals to calculate the mean radius of a 1s orbital.

All s orbitals are spherically symmetric, but differ in the number of radial nodes (n - l (=0 for s orbital)-1).
As n↑, the radius of the spherical, boundary surface that captures a given fraction of the probability also ↑.
 Radial Distribution Function
Total probability of finding the electron anywhere between the two walls of a spherical shell of thickness
dr at a radius r .

for 1s,

• Because r2 = 0 at the nucleus, P(0) = 0. The volume of the shell of

inspection is zero when r = 0.
• As r → ∞ , P® → 0 on account of the exponential term. The wf. has
fallen to zero at great distances from the nucleus.
• The increase in r2 and the decrease in the exponential factor means
that P(r) passes through a maximum at an intermediate radius.
• The maximum of P (r), which can be found by differentiation, marks
the most probable radius (r*) at which the electron will be found, and
for a 1s orbital in hydrogen occurs at r = a0 (= 52.9 pm) , the Bohr radius.
• As n↑ the r*↑ (expansion of the atom).
 The Most Probable Radius

For a 92U, r* = 0.58 pm ?

 p Orbtals
ml= 0

• All p orbitals with ml = 0 have wavefunctions of this form, but f(r) depends on the value of n.
• The wavefunction is zero everywhere in the xy -plane, where z = 0, so the xy -plane is a nodal plane
of the orbital: the wavefunction changes sign on going from one side of the plane to the other.

Net Motion (angular momentum around z-axis)

• The functions correspond to nonzero angular momentum about the z -axis:

• e+iφ corresponds to clockwise rotation when viewed from below,
• e−iφ corresponds to counterclockwise rotation (from the same viewpoint).
• They have zero amplitude where θ = 0 and 180° (along the z -axis) and maximum amplitude at 90°
(the xy -plane).

When draw, use standing waves

 p Orbtals

• These linear combinations are indeed standing waves with no net orbital angular momentum around
the z -axis, as they are superpositions of states with equal and opposite values of ml.
• The px orbital has the same shape as a pz orbital, but it is directed along the x-axis.
• The py orbital is similarly directed along the y-axis.
• The wavefunction of any p orbital of a given shell can be written as a product of x , y , or z and the
same radial function (which depends on the value of n ).
d Orbitals