Bohr’s Correspondence Principle - Michigan State University · Bohr’s Correspondence Principle...

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Bohr’s Correspondence Principle In limit that n →∞, quantum mechanics must agree with classical physics photon 2 i 2 f photon h n 1 n 1 eV 6 . 13 E f = - = In this limit, n i n f , and then f photon electron’s frequency of revolution in orbit. a Extension of Bohr theory to other “Hydrogen-like” atoms

Transcript of Bohr’s Correspondence Principle - Michigan State University · Bohr’s Correspondence Principle...

Bohr’s Correspondence Principle

In limit that n → ∞, quantum mechanics must agree with classical physics

photon2i

2f

photon hn1

n1

eV 6.13E f=

−=

In this limit, ni → nf , and thenf photon → electron’s frequency of revolution in orbit. a

Extension of Bohr theory to other “Hydrogen-like” atoms

Bohr’s Correspondence Principle

In limit that n → ∞, quantum mechanics must agree with classical physics

photon2i

2f

photon hn1

n1

eV 6.13E f=

−=

In this limit, ni → nf , and thenf photon → electron’s frequency of revolution in orbit. a

Extension of Bohr theory to other “Hydrogen-like” atomsHe+, Li++, Be+++, etc. (one electron “orbiting” nucleus of Q = +Ze)

Bohr’s Correspondence Principle

In limit that n → ∞, quantum mechanics must agree with classical physics

photon2i

2f

photon hn1

n1

eV 6.13E f=

−=

In this limit, ni → nf , and thenf photon → electron’s frequency of revolution in orbit. a

Extension of Bohr theory to other “Hydrogen-like” atomsHe+, Li++, Be+++, etc. (one electron “orbiting” nucleus of Q = +Ze)

22

2

422ee

2nn

eV 6.13Z-

2eZkm

n1

E =

−=

h

Bohr’s Correspondence Principle

In limit that n → ∞, quantum mechanics must agree with classical physics

photon2i

2f

photon hn1

n1

eV 6.13E f=

−=

In this limit, ni → nf , and thenf photon → electron’s frequency of revolution in orbit. a

Extension of Bohr theory to other “Hydrogen-like” atomsHe+, Li++, Be+++, etc. (one electron “orbiting” nucleus of Q = +Ze)

22

2

422ee

2nn

eV 6.13Z-

2eZkm

n1

E =

−=

h

Intrinsic linewidth ∆λ of emitted photons

Intrinsic linewidth ∆λ of emitted photons

Ei

Ef ground state

photon

excited state

Intrinsic linewidth ∆λ of emitted photons

Ei

Ef ground state

photon λ==−

hcEEE photonfi

excited state

Intrinsic linewidth ∆λ of emitted photons

Ei

Ef ground state

photon λ==−

hcEEE photonfi

Time-energy uncertainty principle:

excited state

Intrinsic linewidth ∆λ of emitted photons

Ei

Ef ground state

photon λ==−

hcEEE photonfi

Time-energy uncertainty principle:π

≥∆⋅∆4h

tE ii

excited state

Intrinsic linewidth ∆λ of emitted photons

Ei

Ef ground state

photon λ==−

hcEEE photonfi

Time-energy uncertainty principle:π

≥∆⋅∆4h

tE ii

The excited state of an atom is short lived (∆ti ~ 10-8 s ) before a photon is emitted.

excited state

Intrinsic linewidth ∆λ of emitted photons

Ei

Ef ground state

photon λ==−

hcEEE photonfi

Time-energy uncertainty principle:π

≥∆⋅∆4h

tE ii

The excited state of an atom is short lived (∆ti ~ 10-8 s ) before a photon is emitted. This causes an uncertainty in Ei (∆Ei) that induces an uncertainty in Ephoton, which in turn produces an uncertainty in λ.

excited state

Intrinsic linewidth ∆λ of emitted photons

Ei

Ef ground state

photon λ==−

hcEEE photonfi

Time-energy uncertainty principle:π

≥∆⋅∆4h

tE ii

The excited state of an atom is short lived (∆ti ~ 10-8 s ) before a photon is emitted. This causes an uncertainty in Ei (∆Ei) that induces an uncertainty in Ephoton, which in turn produces an uncertainty in λ.

excited state

For Ephoton ~ 2 eV (visible spectrum), ∆λ/λ ~ 10-8.

De Broglie electron waves and the Hydrogen atom

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie standing wavesin an electron orbit

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie standing wavesin an electron orbit

λ=π nr2

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie standing wavesin an electron orbit

λ=π nr2n = 1, 2, 3…

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie standing wavesin an electron orbit

λ=π nr2n = 1, 2, 3…

vmh

e=λ

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie standing wavesin an electron orbit

λ=π nr2n = 1, 2, 3…

vmh

e=λ

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie standing wavesin an electron orbit

λ=π nr2n = 1, 2, 3…

vmh

e=λ

De Broglie electron waves and the Hydrogen atom

nrvme h⋅=⋅⋅Meaning of: ?Analogy with standing waves on a vibrating string—get standing waves if have integer number of λ’s, in this case 3λ.

λ

3λInstead wrap string into circle,standing wave pattern is similar.

De Broglie standing wavesin an electron orbit

λ=π nr2n = 1, 2, 3…

vmh

e=λ

hnrvme =⋅⋅

Quantum Mechanics and the Hydrogen Atom

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

A revision of Bohr theory: n = 1 state actually has zero angular momentum!

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

A revision of Bohr theory: n = 1 state actually has zero angular momentum!

How is this possible? Won’t electron fall into proton?

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

A revision of Bohr theory: n = 1 state actually has zero angular momentum!

How is this possible? Won’t electron fall into proton?

Invoke Heisenberg Uncertainty Principle

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

A revision of Bohr theory: n = 1 state actually has zero angular momentum!

How is this possible? Won’t electron fall into proton?

Invoke Heisenberg Uncertainty PrincipleAs electron is localized near proton, the uncertainty of linear momentum will increase, causing its kinetic energy to rise.

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

A revision of Bohr theory: n = 1 state actually has zero angular momentum!

How is this possible? Won’t electron fall into proton?

Invoke Heisenberg Uncertainty PrincipleAs electron is localized near proton, the uncertainty of linear momentum will increase, causing its kinetic energy to rise.

π≥∆⋅∆

4h

pr r

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

A revision of Bohr theory: n = 1 state actually has zero angular momentum!

How is this possible? Won’t electron fall into proton?

Invoke Heisenberg Uncertainty PrincipleAs electron is localized near proton, the uncertainty of linear momentum will increase, causing its kinetic energy to rise.

Thus electron never “falls” into proton. Instead it forms a spherical “probability cloud” around nucleus.

π≥∆⋅∆

4h

pr r

Quantum Mechanics and the Hydrogen Atom

Schrodinger wave equation was solved for Hydrogen atom

A revision of Bohr theory: n = 1 state actually has zero angular momentum!

How is this possible? Won’t electron fall into proton?

Invoke Heisenberg Uncertainty PrincipleAs electron is localized near proton, the uncertainty of linear momentum will increase, causing its kinetic energy to rise.

“probability cloud”

nucleus

Thus electron never “falls” into proton. Instead it forms a spherical “probability cloud” around nucleus.

π≥∆⋅∆

4h

pr r

n = 1

Quantum Mechanics and the Hydrogen Atom (cont.)Quantum numbers

Quantum Mechanics and the Hydrogen Atom (cont.)Quantum numbers

Quantum Mechanics and the Hydrogen Atom (cont.)Quantum numbers

Need to include Spin Magnetic Quantum Number: ms = ± ½

Quantum Mechanics and the Hydrogen Atom (cont.)Quantum numbers

Need to include Spin Magnetic Quantum Number: ms = ± ½

ms = + ½

Quantum Mechanics and the Hydrogen Atom (cont.)Quantum numbers

Need to include Spin Magnetic Quantum Number: ms = ± ½

ms = + ½

ms = - ½

Pauli Exclusion Principle (1925) and the Periodic TableWolfgang Pauli (1900-1958)

Pauli Exclusion Principle (1925) and the Periodic TableWolfgang Pauli (1900-1958)

No two electrons in an atom can ever be in the same quantum state; that is, no two electrons in the same atom can have exactly the same value for the set of quantum numbers: n, l, ml, ms.

Pauli Exclusion Principle (1925) and the Periodic TableWolfgang Pauli (1900-1958)

No two electrons in an atom can ever be in the same quantum state; that is, no two electrons in the same atom can have exactly the same value for the set of quantum numbers: n, l, ml, ms.

+

+

+

Characteristic X-rays Mo: Z = 42

Characteristic X-rays Mo: Z = 42

n = 1K shell

n = 2L shell

State 1

Characteristic X-rays Mo: Z = 42

n = 1K shell

n = 2L shell

n = 1K shell

n = 2L shell

State 1High energy

electron

Characteristic X-rays Mo: Z = 42

n = 1K shell

n = 2L shell

n = 1K shell

n = 2L shell

State 1

Characteristic X-rays Mo: Z = 42

n = 1K shell

n = 2L shell

n = 1K shell

n = 2L shell

State 1 State 2

Characteristic X-rays Mo: Z = 42

n = 1K shell

n = 2L shell

n = 1K shell

n = 1K shell

n = 2L shell

n = 2L shell

State 1 State 2

Characteristic X-rays Mo: Z = 42

n = 1K shell

n = 2L shell

Eph

n = 1K shell

n = 1K shell

n = 2L shell

n = 2L shell

State 1 State 2 State 3

Characteristic X-rays Mo: Z = 42

n = 1K shell

n = 2L shell

Eph

n = 1K shell

n = 1K shell

n = 2L shell

n = 2L shell

In K shell for State 1, each electron partially shields the other. Thus effective nuclear charge ≡ Zeff = 42 – 1 = 41. In State 2, there is only one electron between L-shell electrons and nucleus, thus Zeff = 42 –1 = 41.

State 1 State 2 State 3

2eff2

2eff

K ZeV 6.13n

ZeV 6.13E ⋅−=⋅−=

2eff2

2eff

K ZeV 6.13n

ZeV 6.13E ⋅−=⋅−=

4Z

eV 6.13n

ZeV 6.13E

2eff

2

2eff

L ⋅−=⋅−=

2eff2

2eff

K ZeV 6.13n

ZeV 6.13E ⋅−=⋅−=

4Z

eV 6.13n

ZeV 6.13E

2eff

2

2eff

L ⋅−=⋅−=

keV 1.17EEE KLph =−=

2eff2

2eff

K ZeV 6.13n

ZeV 6.13E ⋅−=⋅−=

keV 17.1meV 1024.1

Ech 6

phK

⋅×=

⋅=λ

α

4Z

eV 6.13n

ZeV 6.13E

2eff

2

2eff

L ⋅−=⋅−=

keV 1.17EEE KLph =−=

2eff2

2eff

K ZeV 6.13n

ZeV 6.13E ⋅−=⋅−=

keV 17.1meV 1024.1

Ech 6

phK

⋅×=

⋅=λ

α

4Z

eV 6.13n

ZeV 6.13E

2eff

2

2eff

L ⋅−=⋅−=

pm 72K =λα

keV 1.17EEE KLph =−=

2eff2

2eff

K ZeV 6.13n

ZeV 6.13E ⋅−=⋅−=

keV 17.1meV 1024.1

Ech 6

phK

⋅×=

⋅=λ

α

4Z

eV 6.13n

ZeV 6.13E

2eff

2

2eff

L ⋅−=⋅−=

pm 72K =λα

keV 1.17EEE KLph =−=