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Lecture 1 - Quantum & Atomic Structure

Maxwell (1873), proposed that visible light consists of electromagnetic waves. Photon has a frequency of 6. X 104 Hz. Convert this frequency into wavelength (nm) energy (light) is emitted or absorbed in discrete units (quantum)

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71 views

Lecture 1 - Quantum & Atomic Structure

Maxwell (1873), proposed that visible light consists of electromagnetic waves. Photon has a frequency of 6. X 104 Hz. Convert this frequency into wavelength (nm) energy (light) is emitted or absorbed in discrete units (quantum)

Uploaded by

jasumin91
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Quantum Theory and the Electronic Structure of Atoms

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Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Properties of Waves

Wavelength (l) is the distance between identical points on successive waves. Amplitude is the vertical distance from the midline of a wave to the peak or trough. Frequency (n) is the number of waves that pass through a particular point in 1 second (Hz = 1 cycle/s). The speed (u) of the wave = l x n
2

Maxwell (1873), proposed that visible light consists of electromagnetic waves.

Electromagnetic radiation is the emission and transmission of energy in the form of electromagnetic waves.

Speed of light (c) in vacuum = 3.00 x 108 m/s


All electromagnetic radiation lxn=c

A photon has a frequency of 6.0 x 104 Hz. Convert this frequency into wavelength (nm). Does this frequency fall in the visible region?
l

lxn=c n l = c/n l = 3.00 x 108 m/s / 6.0 x 104 Hz l = 5.0 x 103 m l = 5.0 x 1012 nm

Mystery #1, Heated Solids Problem Solved by Planck in 1900


When solids are heated, they emit electromagnetic radiation over a wide range of wavelengths. Radiant energy emitted by an object at a certain temperature depends on its wavelength.

Energy (light) is emitted or absorbed in discrete units (quantum). E=hxn Plancks constant (h) h = 6.63 x 10-34 Js

Mystery #2, Photoelectric Effect Solved by Einstein in 1905


Light has both: 1. wave nature 2. particle nature
Photon is a particle of light

hn

KE e-

hn = KE + W KE = hn - W
where W is the work function and depends how strongly electrons are held in the metal

When copper is bombarded with high-energy electrons, X rays are emitted. Calculate the energy (in joules) associated with the photons if the wavelength of the X rays is 0.154 nm.

E=hxn E=hxc/l E = 6.63 x 10-34 (Js) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m) E = 1.29 x 10 -15 J

Line Emission Spectrum of Hydrogen Atoms

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Bohrs Model of the Atom (1913)


1. e- can only have specific (quantized) energy values 2. light is emitted as emoves from one energy level to a lower energy level

En = -RH (

1 n2

n (principal quantum number) = 1,2,3, RH (Rydberg constant) = 2.18 x 10-18J


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E = hn

E = hn

12

Ephoton = DE = Ef - Ei
ni = 3 ni = 2 nf = 2 ni = 3

1 Ef = -RH ( 2 nf 1 Ei = -RH ( 2 ni 1 DE = RH( 2 ni

) )
1 n2 f

nn =11 f f=
13

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Calculate the wavelength (in nm) of a photon emitted by a hydrogen atom when its electron drops from the n = 5 state to the n = 3 state. Ephoton = DE = RH(

1 n2 i

1 n2 f

Ephoton = 2.18 x 10-18 J x (1/25 - 1/9) Ephoton = DE = -1.55 x 10-19 J Ephoton = h x c / l l = h x c / Ephoton

l = 6.63 x 10-34 (Js) x 3.00 x 108 (m/s)/1.55 x 10-19J


l = 1280 nm
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Why is e- energy quantized?

De Broglie (1924) reasoned that e- is both particle and wave. 2pr = nl


h l = mu

u = velocity of em = mass of e16

What is the de Broglie wavelength (in nm) associated with a 2.5 g Ping-Pong ball traveling at 15.6 m/s?
l = h/mu

h in Js m in kg u in (m/s)

l = 6.63 x 10-34 / (2.5 x 10-3 x 15.6)

l = 1.7 x 10-32 m = 1.7 x 10-23 nm

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Schrodinger Wave Equation


In 1926 Schrodinger wrote an equation that described both the particle and wave nature of the eWave function (y) describes: 1. energy of e- with a given y 2. probability of finding e- in a volume of space Schrodingers equation can only be solved exactly for the hydrogen atom. Must approximate its solution for multi-electron systems.

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Schrodinger Wave Equation


y is a function of four numbers called
quantum numbers (n, l, ml, ms)
principal quantum number n n = 1, 2, 3, 4, . distance of e- from the nucleus

n=1

n=2

n=3

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Where 90% of the e- density is found for the 1s orbital

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Schrodinger Wave Equation


quantum numbers: (n, l, ml, ms)

angular momentum quantum number l


for a given value of n, l = 0, 1, 2, 3, n-1 l=0 l=1 l=2 l=3 s orbital p orbital d orbital f orbital

n = 1, l = 0 n = 2, l = 0 or 1 n = 3, l = 0, 1, or 2

Shape of the volume of space that the e- occupies


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l = 0 (s orbitals)

l = 1 (p orbitals)

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l = 2 (d orbitals)

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Schrodinger Wave Equation


quantum numbers: (n, l, ml, ms) magnetic quantum number ml for a given value of l ml = -l, ., 0, . +l if l = 1 (p orbital), ml = -1, 0, or 1 if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2 orientation of the orbital in space
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ml = -1, 0, or 1

3 orientations is space

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ml = -2, -1, 0, 1, or 2

5 orientations is space

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Schrodinger Wave Equation


(n, l, ml, ms) spin quantum number ms ms = + or -

ms = +

ms = -

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Schrodinger Wave Equation


quantum numbers: (n, l, ml, ms) Existence (and energy) of electron in atom is described by its unique wave function y. Pauli exclusion principle - no two electrons in an atom can have the same four quantum numbers.

Each seat is uniquely identified (E, R12, S8) Each seat can hold only one individual at a time
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Schrodinger Wave Equation


quantum numbers: (n, l, ml, ms) Shell electrons with the same value of n Subshell electrons with the same values of n and l

Orbital electrons with the same values of n, l, and ml


How many electrons can an orbital hold? If n, l, and ml are fixed, then ms = or -

y = (n, l, ml, ) or y = (n, l, ml, -)


An orbital can hold 2 electrons
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How many 2p orbitals are there in an atom?


n=2 If l = 1, then ml = -1, 0, or +1

2p
l=1

3 orbitals

How many electrons can be placed in the 3d subshell? n=3 3d l=2

If l = 2, then ml = -2, -1, 0, +1, or +2


5 orbitals which can hold a total of 10 e31

Energy of orbitals in a single electron atom


Energy only depends on principal quantum number n

n=3 n=2

En = -RH (

1 n2

n=1
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Energy of orbitals in a multi-electron atom


Energy depends on n and l

n=3 l = 2
n=3 l = 0 n=2 l = 0 n=3 l = 1

n=2 l = 1

n=1 l = 0
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Fill up electrons in lowest energy orbitals (Aufbau principle)

?? Be Li B5 C 3 64 electrons electrons 22s 2 2 22p 1 21 BBe Li 1s 1s 1s 2s 2s H 12 electron He electrons


12 He H 1s 1s
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The most stable arrangement of electrons in subshells is the one with the greatest number of parallel spins (Hunds rule).

Ne C N O F 9 6 7 810 electrons electrons electrons 2 22s 22s 2 22p 22p 5 2 3 46 Ne C N O F 1s 1s

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Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s 36

Electron configuration is how the electrons are distributed among the various atomic orbitals in an atom.
number of electrons in the orbital or subshell

1s1
principal quantum number n angular momentum quantum number l

Orbital diagram
H 1s1
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What is the electron configuration of Mg? Mg 12 electrons 1s < 2s < 2p < 3s < 3p < 4s 1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons [Ne] 1s22s22p6

Abbreviated as [Ne]3s2

What are the possible quantum numbers for the last (outermost) electron in Cl? Cl 17 electrons 1s22s22p63s23p5 1s < 2s < 2p < 3s < 3p < 4s 2 + 2 + 6 + 2 + 5 = 17 electrons

Last electron added to 3p orbital

n=3

l=1

ml = -1, 0, or +1

ms = or -

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Outermost subshell being filled with electrons

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Paramagnetic

Diamagnetic

unpaired electrons 2p

all electrons paired


2p

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