Orbitals of Hydrogenic Atom

The orbitals for the hydrogenic atom are given by (r, , ) R(r)nl Yl,m ( , ) ; n = 1, 2, 3 ... l < n - 1; m = - l, - l + 1, ....l - 1, l

Where 2l + 1 (l | m! | |m| ( , ) = Yl,m (( , ) = Pl (cos ) exp[im ] 4 (l | m!|) are eigenfunctions to L2 and L z

and Rnl solution to h 2 2Rnl (r) { 2 2 r 2 Rnl (r) Ze ) { r 4 or r h2l(l 1) 2 mr

2

}Rnl (r)

EnRnl (r)

Hydrogen Levels

1, l = 0 n,l,m ( , ) = Rnl (r)Yl,m (( , )

3/ 2 3/ 2 e

Z /2 R1, 0 (r) 2 Z R1, 0 (r) 2 a o e /2 ao No nodes. R1,0 (r) everywhere positive For l = 0 we have m = 0; 1 Yo,o 4

1s orbital

Value of Yoo is uniform over sphere

Orbitals of Hydrogenic Atom

The balance of kinetic and potential energies that accounts for the structure of the ground state of hydrogen (and similar atoms).
(b) the mean kinetic energy is low, but the potential energy is not very favourable;

; (c) the compromise of moderate kinetic energy and moderately favourable potential energy. (a) The sharply curved but localized orbital has high mean kinetic energy, but low mean potential energy

Orbitals of Hydrogenic Atom n no, l = 0 n,l,m ( , ) = Rnl (r)Yl,m (( , )

For l = 0 we have m = 0; 1 Yo,o 4

Z 2 2 ao 1 Z 9 3 ao 1
3/ 2

R20 (r)

(2
3/ 2

1 )e 2 1 9

/4

R30 (r)

(6 2

)e

/6

One node at 1 (2 ) 0 2 with = 2Zr/a o ; node : 2ao / Z

two nodes at 1 2 (6 2 ) 0 9 with = 2Zr/ao ; nodes : 1.9ao / Z and 7.1Zr/ao

Orbitals of Hydrogenic Atom

no, l = 0 Why has Rnl (r) n- 1 nodes ? no ,o,o ( , ) = Rno ,o (r)Yo,o (( , )

jdv

We have seen previously that any two independent solutions to the Schrdinger equation must be orthogonal :

ij

Thus any two s - orbitals Rn'o Yoo and Rno Yoo must be orthorgonal
2

Rn'o YooRn'o Yoodv

0 00

Orbitals of Hydrogenic Atom

2

Rn'oYooRn'oYoodv
0 00 2 r

Yoo Yoo sin d d

o o
r

Rn'o (r)Rno (r)r2 dr

0
0

1
o

R n'o (r)Rno (r)r 2dr

Yoo normalized
The R1o function is positive every where R1, 0 (r) Z 2 ao
3/ 2

/2

Thus for R2o to R1o

r o

Orbitals of Hydrogenic Atom to be orthogonal

R1o (r)R 2o (r)r2 dr

For R3o to be orthogonal to R1o and R20 two nodes are required etc...

R20 must have positive and negative regions

Z 2 2 ao 1
3/ 2

R20 (r)

1 )e (2 2

/4

Orbitals of Hydrogenic Atom

The probability density Pnlm (r, , ) = nlmr, , )

nlmr,

, )

P1,00 (r, . ) Z 2 ao
3/2

Z 2 ao
/2

3/ 2

e 1 Z ao

/2

Yoo e

Yoo

A constant-volume electron-sensitive detector (the small cube) gives its greatest reading at the nucleus, and a smaller reading elsewhere. The same reading is obtained anywhere on a circle of given radius: the s orbital is spherically symmetrical.

Orbitals of Hydrogenic Atom

Representations of the 1s and 2s hydrogenic atomic orbitals in terms of their electron densities (as represented by the density of shading).
The probability density Pnlm (r, , ) = nlmr, , )
nlmr,

, )

P1,00 (r)

1 Z ao 1 32 Z ao

P2o0 (r)

(2

1 2 ) e 2

/2

Orbitals of Hydrogenic Atom An aside How do we plot Ylm ? Calculate the value of Ylm ( , ) r at the position of each en e1 (e.i for each n , n ). Construct e4 e 3 the vectors : R1 , R2 , R3 , . .Rn r r where : Rn enYlm ( , )

Draw Rn
e e 5 2
R3 R 1 R4

Consider a unit sphere withradius 1. Draw a large number ofunit vectors from the origin ofthe sphere in different directions r r r (e.i. different , ) e1 , e 2 , e 3 , r r e4 ...en

R5 R2

Orbitals of Hydrogenic Atom

R4 R3 R 1

An aside

R5 R2

Draw a surface through the r endpoints of all Rn . This surface represents Ylm ( , )

Orbitals of Hydrogenic Atom

An aside

For Yoo ( , ) we have r Rn 1 r en for all n

THus Yoo representing the angular part of a ns function is represented by a sphere

ns - orbital

We have that Yoo ( , ) is spherical e.u. the same for all n , n

Orbitals of Hydrogenic Atom

The boundary surface of an s orbital, within which there is a 90 per cent probability of finding the electron.

Orbitals of Hydrogenic Atom

Mean radius

The mean radius is given as the espectation value

r
nlmr nlmdv

For the hydrogenic atom < r >nl n2 1 1 l(l 1) ao (1 2 Z n2

The variation of the mean radius of a hydrogenic atom with the principal and orbital angular momentum quantum numbers. Note that the mean radius lies in the order d p s for a given value of n.

Orbitals of Hydrogenic Atom

A constant-volume electron-sensitive detector (the small cube) gives its greatest reading at the nucleus, and a smaller reading elsewhere. The same reading is obtained anywhere on a circle of given radius: the s orbital is spherically symmetrical.

P1,00 (r, . ) 2 Z ao
3/ 2

Z 2 ao
/2

3/2

e 1 Z ao

/2

Yoo e

Yoo

Orbitals of Hydrogenic Atom

The radial distribution function P gives the probability that the electron will be found anywhere in a shell of radius r. For a 1s electron in hydrogen, P is a maximum when r is equal to the Bohr radius a0. The value of P is equivalent to the reading that a detector shaped like a spherical shell would give as its radius was varied.

Orbitals of Hydrogenic Atom Radial probability density

The probability of finding the electron between r and r + dr is :
2

Pnl (r)dr
o o 2 o o 2 o o

Pnlm (r, , )dv

Pnlm (r, , )rsin d d r2dr | R nl ((r) |2 Ylm ( , ) |2 sin d d r 2dr 1 | Rnl ((r) |2 r2 dr

Thus the radial probability density is Pnl (r) | Rnl ((r)|2 r 2

Orbitals of Hydrogenic Atom Radial probability density

The radial probability density is Pnl (r) | Rnl ((r)|2 r2 The most probable radius corrsponds to the maxima for Pnl (r). For 1s r
r

ao Z

Orbitals of Hydrogenic Atom

Orbitals with increasing l are called
n1m

Rn1(r)Y1m ( , ) p - orbitals
R n2 (r)Y2m ( , ) d - orbitals

m = - 1, 0, 1
m = - 2, -1, 0, 1, 2

n2m

n3m

R n3 (r)Y3m ( , ) f - orbitals

m = - 3, -2, -1, 0, 1, 2, 3

Structure of Hydrogenic Atoms Orbitals of Hydrogenic Atom Rnl is a solution to

h 2 2Rnl (r) { 2 2 r

2 Rnl (r) Ze ) { r 4 or r

h2l(l 1) 2 mr
2

}Rnl (r)

ERnl (r)

Veff

2 mr2 becomes more repulsive near nucleus at small r. Hence Rnl (r) tend to zero as r o with increasing spead as l becomes larger

As l increases the ve centrigugal term

h 2l(l 1)

Structure of Hydrogenic Atoms

The asymptotic behaviour of the radial s, p, and d functions differ as a result of the centrifugal term in the radial Schrdinger equation
3/2 3/ 2

R1, 0 (r)

Z ao

Zr / r

for r

; 1s

Z ao

R21(r)

Z 1 2 6 ao

5 /2

re
7/ 2

Zr / 2a o

for r

; 2p

R3,2 (r)

Z 4 81 30 a o

r 2e

Zr / 4a o

for r

; 3p

r2

Orbitals of Hydrogenic Atom

Close to the nucleus, p orbitals are proportional to r, d orbitals are proportional to r2, and f orbitals are proportional to r3. Electrons are progressively excluded from the neighbourhood of the nucleus as l increases. An s orbital has a finite, nonzero value at the nucleus.

Orbitals of Hydrogenic Atom Let us now look at the angular part of the p - functions

, ) n = 2, l = 1
211(r, , )

nlm (r,

R(r)nl Yl,m ( , )

m
3 8

1, 0, 1
1/ 2

R(r)21Y1,1( , ) = -R(r)21

sin ei

210 (r,

, )

R(r)21Y1,0 ( , ) = R(r)21

3 4
3 8

1/ 2

cos

1/2

21

1(r, , )

R(r)21Y1,-1( , ) = R(r)21

sin e

Orbitals of Hydrogenic Atom

211(r, , )

-R(r)21

3 8

1/ 2

sin ei

l = 1, m = 1

r The electron has an angular momentum L such that L L = h 2l(l 1) s The z - component of L is L z
v L z r v r v v y v xL
2

h
z Lz y h 2l(l 1) x hml

Orbitals of Hydrogenic Atom

210 (r,

, ) = R(r)21

r The electron has an angular momentum L such that L L = h 2l(l 1) s The z - component of L is L z o

3 4

1/ 2

cos

l = 1, m = 0

z Lz L2 h 2l(l 1) y x hml
m=0

Orbitals of Hydrogenic Atom

21 1(r, , ) = R(r)21

3 8

1/ 2

sin e

l = 1, m = -1

r The electron has an angular momentum L such that L L = h 2l(l 1) s The z - component of L is L z h

z L2 h 2l(l 1)

y x
m=-1

Lz

hml

Orbitals of Hydrogenic Atom Plotting angular part of

210 (r,

, ) = R(r)21

3 4

1/ 2

cos

2p z

k cos
+

r Draw vector R of length kcos through each point ( , ) on sphere

Draw surface through all vectors R

Orbitals of Hydrogenic Atom

The remaining two orbitals are complex

211(r,

, )

-R(r)21

3 8 3 8

1/2

sin [cos
1/ 2

i sin ] i sin ]

21 1(r,

, ) = R(r)21

sin [cos

However by linear combinations we can get the real orbitals

2px

1 { 2 i { 2

211 -

21 1} = R(r)21

3 8 3 8

1/ 2

sin cos
1/2

2py

211 +

21 1}

= R(r)21

sin sin

Orbitals of Hydrogenic Atom

2px 2py

1 { 2 i { 2

211 -

21 1}

= R(r)21 = R(r)21

3 8 3 8

1/ 2

sin cos
1/2

211 +

21 1}

sin sin

The orbitals 2p x and 2p y have the same energies and eigenvalues to L2 as

211

and

21-1

. However only the latter are eigenfunctions of L z

z

+ -

y x +

2py

2px

Orbitals of Hydrogenic Atom

The boundary surfaces of p orbitals. A nodal plane passes through the nucleus and separates the two lobes of each orbital. The dark and light areas denote regions of opposite sign of the wavefunction.

Orbitals of Hydrogenic Atom

Orbitals of Hydrogenic Atom

In transitions between different energy levels of the hydrogenic atom the following selection rules apply l= 1 m = o,

A Grotrian diagram that summarizes the appearance and analysis of the spectrum of atomic hydrogen. The thicker the line, the more intense the transition.