Hydrogen Atom

• The series of atoms/ions H, He+, Li2+, Be3+ …

all have: 1 electron (charge –e)
nucleus (charge +Ze)

• To determine the electronic wavefunction (y = ye) and allowed electronic energy levels (E), we
must set up and solve the Schrödinger Equation for a single electron in an atom.

-e
me
+Ze
mN
• Consider 3-D motion of the electron (-e) relative to the nucleus (+Ze):

Hamiltonian Operator ˆ =T
H ˆ +V
ˆ

!2 2 me × m N
Kinetic Energy T̂ = - Ñ where µ= » me
2µ me + m N
2
ˆ = V(r ) = - Ze
Potential Energy V where
r = x2 + y2 + z2
4pe 0 r
(electrostatic attraction between electron and nucleus).

-e
æ ¶ 2
¶ ¶ 2 2 ö r me
Ñ2 = ç 2 + 2 + 2 ÷
ç ¶x ¶y ¶z ÷
è ø +Ze
mN
• We must solve the 2nd order differential equation:
!2 2
- Ñ ψ + V(r )ψ = Eψ
2µ
• Because of the spherical symmetry of the atom, it is convenient to describe the position of the electron in
spherical polar coordinates (r,q,f), rather than Cartesians (x,y,z).
• Due to this spherical symmetry, the wavefunction can be separated into a product of radial and angular
components:
y(r,q,f) = R(r).Y(q,f)

• Imposing boundary conditions Þ 3 quantum numbers (n, !, m!)

Þ yn,!,m!(r,q,f) = Rn,!(r).Y!,m!(q,f)
angular
radial
wavefunction
wavefunction
(spherical harmonic)
Quantum Numbers

yn,!,m!(r,q,f) = Rn,!(r).Y!,m!(q,f)

• y depends on 3 quantum numbers (n, !, m!).

1. Principal Quantum Number (n)

• Positive integer n = 1, 2, 3 …
• For H and 1-e ions, the electron energy depends only on n

æ µe 4 ö æ Z2 ö
E n = -ç 2 2 ÷×ç ÷
ç 8h e ÷ ç n2 ÷
è 0 ø è ø
2. Orbital Angular Momentum Quantum Number (!)

• For a given value of n, ! can take the integer values:

! = 0, 1, 2 … (n-1)
e.g. n = 1 !=0
n=2 ! = 0, 1
n=3 ! = 0, 1, 2

3. Orbital Magnetic Quantum Number (m!)

• For a given value of !, m! can take the integer values:

m! = 0, ±1, ±2 … ± !

e.g. ! = 0 m! = 0
!=1 m! = 0, ±1

• There are (2!+1) allowed values of m!.

 1 0 0 1s c1s 5 a b e2s
!p a0
Table 12.1
1 Z 3/2
Solutions of the Schrödinger Wave Equation for a One-Electron Atom 2 0 0 2s c2s 5 a b 12 2 s2 e2s/2
4!2p a0
n ! m! Orbital Solution
1 Z 3/2
2 1 0 2pz c2pz 5 a b se2s/2 cos u
1 Z 3/2 2s 4!2p a0
1 0 0 1s c1s 5 a b e
!p a0
1 Z 3/2
1 Z 3/2 2 1  2px c2px 5 a b se2s/2 sin u cos f
2 0 0 2s c2s 5 a b 12 2 s2 e2s/2  4!2p a0
4!2p a0 "1 
 2p 1 Z 3/2
1 Z 3/2
 y c2py 5 a b se2s/2 sin u sin f
2 1 0 2pz c2pz 5 a b se2s/2 cos u 4!2p a0
4!2p a0
1 Z 3/2
1 Z 3/2 3 0 0 3s c3s 5 a b 127 2 18s 1 2s22 e2s/3
2 1  2px c2px 5 a b se2s/2 sin u cos f 81!3p a0
 4!2p a0
"1  !2 Z 3/2
 2p 1 Z 3/2 3 1 0 3pz c3pz 5 a b 16s 2 s22 e2s/3 cos u
 y c2py 5 a b se2s/2 sin u sin f 81!p a0
4!2p a0
1 Z 3/2 !2 Z 3/2
3 0 0 3s c3s 5 a b 127 2 18s 1 2s22 e2s/3 3 1  3px c3px 5 a b 16s 2 s22 e2s/3 sin u cos f
81!3p a0  81!p a0
"1 
!2 Z 3/2  3p !2 Z 3/2
3 1 0 3pz c3pz 5 a b 16s 2 s22 e2s/3 cos u  y c3py 5 a b 16s 2 s22 e2s/3 sin u sin f
81!p a0 81!p a0
!2 Z 3/2 1 Z 3/2
3 1  3px c3px 5 a b 16s 2 s22 e2s/3 sin u cos f 3 2 0 3dz2 c3dz 5 a b s2e2s/3 13 cos2 u 2 12
 81!p a0 2

81!6p a0
"1 
 3p !2 Z 3/2 !2 Z 3/2 2 2s/3
 y c3py 5 a b 16s 2 s22 e2s/3 sin u sin f 3 2  3dxz c3dxz 5 a b se sin u cos u cos f
81!p a0 81!p a0

1 Z 3/2 "1 
3 2 0 3dz2 c3dz 5 a b s2e2s/3 13 cos2 u 2 12  !2 Z 3/2 2 2s/3
81!6p a0  3dyz c3dyz 5 a b se sin u cos u sin f
2

81!p a0
!2 Z 3/2 2 2s/3
3 2  3dxz c3dxz 5 a b se sin u cos u cos f 1 Z 3/2
 81!p a0 3 2  3dxy c3dxy 5 a b s2e2s/3 sin2 u sin 2f
"1   81!2p a0
 !2 Z 3/2 2 2s/3 "2 
 3dyz c3dyz 5 a b se
81!p a0
sin u cos u sin f  1 Z 3/2
 3dx2#y2 c3dx 2 y 5 a b s2e2s/3 sin2 u cos 2f
81!2p a0
2 2

1 Z 3/2
3 2  3dxy c3dxy 5 a b s2e2s/3 sin2 u sin 2f Note: ! ! Zr/a0, where Z ! 1 for hydrogen; a0 ! "0h2/#me2 ! 5.29 $ 10#11 m.
 81!2p a0
"2  3/2
 1 Z 2 2s 3 2
Atomic Orbitals

• The wavefunctions (yn,!,m!) describing an electron in an atom are known as atomic

orbitals.

• Each atomic orbital (1-e wavefunction) is uniquely defined by 3 quantum numbers

(n,!,m!).

• The orbital (y) gives the spatial distribution of the electron (via the Born interpretation
of |y|2).

• Orbitals are often drawn as 3-D surfaces which enclose approx. 90% of the probability
of finding the electron.
 Quantum Numbers and Atomic Orbitals

• Orbitals differ from each other in size, shape and orientation:

– the orbital size is defined by the principle quantum number n

– the type of orbital (it’s shape) is defined by the angular momentum quantum number !

– the orientation of the orbital is defined by the orbital magnetic quantum number m!
 Shape of Atomic Orbitals
Shape – determined by the angular wavefunction Y!,m!(q,f)

1s orbital (n = 1, ! = 0)
32
1 æ 1 ö
• Normalized wavefunction: y(1s ) = ç
ç
÷
÷ e -r a 0
p è a0 ø
• Has no angular dependence
(spherically symmetric, depends only on r).
+
• All s orbitals are spherically symmetrical.

2s orbital ns orbital
y(2s ) µ (2 - r ) e - r 2 y(ns ) µ f (r ) e - r n

• As n­, orbitals expand – average radius árñ­

2p orbitals (n = 2, ! = 1)

• There are 3 degenerate orbitals, with 3 different m! values

(0,±1).

• e.g. m! = 0 Þ 2pz orbital (pointing along z-axis)

52
y(2p z ) =
1 æ 1
ç
ö
÷ × rcosq × e - r 2a 0
+ -
ç
4 2p è a 0
÷
ø - +

• m! = ±1 Þ 2px, 2py orbitals -

+
Atomic Orbitals

The p orbitals:

Three orientations:
l = 1 (as required for a p orbital)
ml = –1, 0, +1
Atomic Orbitals

The d orbitals:

Five orientations:
l = 2 (as required for a d orbital)
ml = –2, –1, 0, +1, +2
 Electronic Shells, Sub-shells and Orbitals

3d orbitals
l=2 ml =2 ml =1 ml =0 ml =-1 ml =-2

n=3
3p orbitals
l=1 ml =1 ml =0 ml =-1

3s orbital
l=0 ml =0

shell sub-shells orbitals

 !
Beyond f the letters become alphabetic: !"0 !"1 !"2 !"3 !"4
g, h, . . . , skipping j, which is reserved
INTERACTIVE
as a symbolEXAMPLE 12.7
for angular momentum. 5s 5p 5d 5f 5g ◀
Electron Subshells
Numberlevel
For principal quantum of Orbitals
n " 5, determine the number of subshells (differ-
ent values of !) and give the designation of each. The first four levels of orbitals in the hydrogen atom are listed with their
per Subshell
s"1 quantum numbers in Table 12.3 ▼. Note that each set of orbitals with a given
Solution For n " 5 the allowed values of ! runvalue
from 0
ofto! 4(sometimes
(n ! 1 " 5 called
! 1). a subshell) is designated by giving the value of n
p"3
Thus the subshells and their designations are and the letter for !. ◀ Thus an orbital where n " 2 and ! " 1 is symbolized as
d"5
! " 0 f "!7" 1 !"2 ! 2p.
" 3 There
!" are
4 three 2p orbitals, which have different orientations in space. We
g"9 will describe these orbitals in the next section.
5s 5p 5d 5f 5g ◀

The first four levels of orbitals in the hydrogen Table

atom12.3
are listed with their
quantumnnumbers
" 1, 2, 3,in . .Table
. 12.3 ▼. Note that each set of orbitals
Quantum Numbers with
for athe
given
First Four Levels of Orbitals in the Hydrogen Atom ◀
value of !! "(sometimes called
0, 1, . . . , (n ! 1) a subshell) is designated by giving the value of n
and themletter for. !. Thus
. .◀, 0, . . . an
, #!orbital where n " 2 and ! " 1 is symbolized asOrbital Number of
! " !!,
2p. There are three 2p orbitals, which have different n !
orientations Designation
in space. We m! Orbitals
will describe these orbitals in the next section.
1 0 1s 0 1
2 0 2s 0 1
Table 12.3 1 2p !1, 0, #1 3
3 0 3s 0 1
Quantum Numbers for the First Four Levels of Orbitals in the Hydrogen Atom ◀
1 3p !1, 0, 1 3
Orbital 2 Number 3dof !2, !1, 0, 1, 2 5
n ! Designation 4!
m 0 4s
Orbitals 0 1
1 4p !1, 0, 1 3
1 0 1s 0 1
2 4d !2, !1, 0, 1, 2 5
2 0 2s 0 1
1 2p !1, 0, #1
3 3
4f !3, !2, !1, 0, 1, 2, 3 7
3 0 3s 0 1
 Atomic Orbital Energy Diagram for H

• Orbital energies depend only on the principal quantum

number n.

• For a given n value (shell), all sub-shells (!) and orbitals

(m!) have the same energy
– i.e. they are degenerate.
 Electron Spin
• Stern and Gerlach (1921) observed that a beam of Ag atoms is split into 2 beams by an
inhomogeneous magnetic field.

• Dirac (1930) introduced relativistic effects into Quantum Mechanics and showed that to
completely describe the state of an electron we must specify:
1. The orbital (yn,!,m!)
2. The spin state of the electron

• Electron spin is characterised by 2 quantum numbers:

– spin angular momentum q. no. s ( = ½ for all electrons)
– spin magnetic q. no. ms ( = ±½).
• Spin angular momentum (S) has magnitude:
3!
S = s(s + 1)! =
2

• The projection of S on the z-axis:

Sz = ms" = ±½ "

• There are two possible electron spin states:

ms = +½ “spin up” ­
ms = -½ “spin down” ¯

• Spin is an intrinsic property of the electron and is not connected with orbital motion.

• Complete specification of an electron in an atom requires 4 quantum numbers (n,!,m!,ms) – as s is

fixed.
Quantum Numbers (QN)

Principal QN:

n = 1, 2, 3, 4……

Angular momentum QN:

l = 0, 1, 2, 3…. (n -1)

Rule: l = (n - 1)

Magnetic QN:

ml = …-2, -1, 0, 1, 2, ..

Rule: -l….0….+l
 Many-Electron Atoms
• For atoms with 2 or more electrons, the Schrödinger Eqn. must include KE terms for all electrons
and PE terms for all e-e and e-n interactions.

• Example: He (2 electrons)
2 terms in T̂
3 terms in V̂
-e(1)
r1
r12
Z = +2e -e(2)
S.E. r2
!2 !2 2 ç
æ 2e 2 2e 2 e2 ö
- 2
Ñ1 - Ñ2 + - - + ÷y = Ey
ç ÷
2m e 2m e è 4pe 0 r1 4pe 0 r2 4pe 0 r12 ø
where
æ ¶ 2y ¶ 2y ¶ 2y ö
Ñ i2 =ç 2 + 2 + 2 ÷
ç ¶x ¶y i ¶z i ÷ø
è i
• For N electrons: YN = Y(r1,r2,r3 … rN)

• For more than 1 e, S.E. cannot be solved analytically – though good numerical
solutions may be obtained from computer calculations.

Þ Approximations must be made.

The Orbital Approximation

• The total wavefunction (YN) for the N-electron atom is approximated by the
product of N 1-e orbitals similar to those of hydrogenic ions:

YN = Y(r1,r2,r3 … rN) = y(r1)y(r2)y(r3)…y(rN)

 Bonding in Molecules
Exact solution of the Schrödinger Equation is not possible for any molecule – even the simplest
molecule H2+.
e
rA rB

HA RAB HB

Full Hamiltonian operator for H2+ :

KE PE

( ) æ 1 1 ö
2 2 2
ˆ =- ! ! e e2
H 2 2
ÑA + ÑB - 2
Ñe - çç + ÷÷ +
2m p 2m e 4pe 0 è rA rB ø 4pe 0 R AB
nuclear K.E. electron K.E. e-n attraction n-n repulsion
 Limitations
• Schrödinger Equation can only be solved exactly for simple systems.
• Rigid Rotor, Harmonic Oscillator, Particle in a Box, Hydrogen Atom

• For more complex systems (i.e. many electron atoms/molecules) we need to make some
simplifying assumptions/approximations and solve it numerically.

• However, it is still possible to get very accurate results (and also get very crummy
results).
• In general, the “cost” of the calculation increases with the accuracy of the calculation and the size of the
system.
Yttrium catalyzed rearrangement of acetylene
40

2A

20

Energy (kcal/mol) 2A’

2B
2
2A
-20 1
2B 2A’ 2A
2 2 2

B
-40 2
2A
1

-60

Reaction Coordinate
 Tools
• There exist a large number of software packages capable of performing
electronic structure calculations.
• MOLPRO, GAMESS, COLUMBUS, NWCHEM, MOLFDIR, ACESII, GAUSSIAN, ...

• The different programs have various advantages and capabilities.

• We also have available to us Gaussview which is a GUI that interfaces with

Gaussian for aiding in building molecules and viewing output.