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Quantum Theory and the Electronic Structure of Atoms Chapter 7

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Properties of Waves Wavelength ( ) is............................................................... Amplitude is...................................................................... Frequency ( ) is....................................................................... The speed (u) of the wave =

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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 =............................ m/s 7.1

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A photon has a frequency of 6.0 x 10 4 Hz. Convert this frequency into wavelength (nm). Does this frequency fall in the visible region? 7.1

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Mystery #1, “Black Body Problem” Solved by Planck in 1900 Energy (light) is emitted or absorbed in discrete units (quantum). 7.1

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Light has both: 1.wave nature 2.particle nature h = KE + BE Mystery #2, “Photoelectric Effect” Solved by Einstein in 1905 Photon is a “particle” of light KE = h - BE h KE e - 7.2

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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. Line Emission Spectrum of Hydrogen Atoms

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1.e - can only have specific (quantized) energy values 2.light is emitted as e - moves from one energy level to a lower energy level Bohr’s Model of the Atom (1913) E n = -R H ( ) 1 n2n2 n (principal quantum number) = 1,2,3,… R H (Rydberg constant) = 2.18 x 10 -18 J E = h

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E photon = E = E f - E i E f = -R H ( ) 1 n2n2 f E i = -R H ( ) 1 n2n2 i i f E = R H ( ) 1 n2n2 1 n2n2 n f = 1 n i = 2 n f = 1 n i = 3 n f = 2 n i = 3 7.3

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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.

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De Broglie (1924) reasoned that e - is both particle and wave. Why is e - energy quantized? 7.4 u = velocity of e- m = mass of e- 2 r = n = h mu

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

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Schrodinger Wave Equation In 1926 Schrodinger wrote an equation that described both the particle and wave nature of the e - Wave function ( ) describes: 1. energy of e - with a given 2. probability of finding e - in a volume of space Schrodinger’s equation can only be solved exactly for the hydrogen atom. Must approximate its solution for multi-electron systems. 7.5

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Schrodinger Wave Equation fn(n, l, m l, m s ) principal quantum number n n = 1, 2, 3, 4, …. n=1 n=2 n=3 7.6 distance of e - from the nucleus

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Where 90% of the e - density is found for the 1s orbital 7.6

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= fn(n, l, m l, m s ) angular momentum quantum number l for a given value of n, l = 0, 1, 2, 3, … n-1 n = 1, l = 0 n = 2, l = 0 or 1 n = 3, l = 0, 1, or 2 Schrodinger Wave Equation 7.6

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l = 0 (s orbitals) l = 1 (p orbitals) 7.6

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l = 2 (d orbitals) 7.6

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= fn(n, l, m l, m s ) magnetic quantum number m l for a given value of l m l = -l, …., 0, …. +l if l = 1 (p orbital), m l = -1, 0, or 1 if l = 2 (d orbital), m l = -2, -1, 0, 1, or 2 Schrodinger Wave Equation 7.6

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m l = -1m l = 0m l = 1 m l = -2m l = -1m l = 0m l = 1m l = 2 7.6

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= fn(n, l, m l, m s ) spin quantum number m s m s = +½ or -½ Schrodinger Wave Equation m s = -½m s = +½ 7.6

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Existence (and energy) of electron in atom is described by its unique wave function . Pauli exclusion principle - no two electrons in an atom can have the same four quantum numbers. Schrodinger Wave Equation = fn(n, l, m l, m s )

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7.6

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Schrodinger Wave Equation = fn(n, l, m l, m s ) 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 m l How many electrons can an orbital hold? If n, l, and m l are fixed, then m s = ½ or - ½ = (n, l, m l, ½ ) or = (n, l, m l, - ½ ) An orbital can hold 2 electrons 7.6

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How many 2p orbitals are there in an atom? 2p n=2 l = 1 If l = 1, then m l = -1, 0, or +1 3 orbitals How many electrons can be placed in the 3d subshell? 3d n=3 l = 2 If l = 2, then m l = -2, -1, 0, +1, or +2 5 orbitals which can hold a total of 10 e - 7.6

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Energy of orbitals in a single electron atom Energy only depends on principal quantum number n E n = -R H ( ) 1 n2n2 n=1 n=2 n=3 7.7

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Energy of orbitals in a multi-electron atom Energy depends on n and l n=1 l = 0 n=2 l = 0 n=2 l = 1 n=3 l = 0 n=3 l = 1 n=3 l = 2 7.7

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“Fill up” electrons in lowest energy orbitals (Aufbau principle) 7.9

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The most stable arrangement of electrons in subshells is the one with the greatest number of parallel spins (Hund’s rule). 7.7

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Order of orbitals (filling) in multi-electron atom 7.7

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Electron configuration is how the electrons are distributed among the various atomic orbitals in an atom. 1s 1 Orbital diagram H 1s 1 7.8

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What is the electron configuration of Mg? What are the possible quantum numbers for the last (outermost) electron in Cl? Cl 17 electrons

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Outermost subshell being filled with electrons 7.8

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Paramagnetic unpaired electrons 2p Diamagnetic all electrons paired 2p 7.8

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