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Chem6A_F11 Hol - Chapter 7 Lecture Slides

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7.1 The Nature of Light

!! Three phenomena could not be explained by classical physics: blackbody radiation, photoelectric effect, and atomic spectra. A new picture of energy was required. !! Blackbody Radiation: Heat a solid object: at 1000 K it begins to emit soft red light; at 1500 K it begins to glow orange and is brighter; at 2000 K it is still brighter and white. How do we explain this? !! Planck: proposed that only certain quantities of energy could be emitted or absorbed:

!! These packets of energy are called quanta, and n is a quantum number. Since it was (correctly) assumed that most transitions occur between adjacent states, !n = 1 and the change in energy is: !

Chem 6A - Chapter 7

Light is Electromagnetic Radiation that is visible to the human eye, and consists of waves. The amplitude of a wave refers to the maximum amount of displacement of a particle from its rest position.

The wavelength of a wave is simply the length of one complete wave cycle. The basic unit of light or electromagnetic radiation is a photon. A photon is a discrete bundle of electromagnetic energy.

Energy of a Photon: h = Plancks constant: h = 6.626 x 10-34 J-sec Frequency (nu) = cycles per second Wavelength (lambda) = distance (meters) per cycle

Chem 6A - Chapter 7

Traveling waves are distinguished by the whole wave, including nodes, propagating at a given velocity. Shown is a traveling wave moving to the right & one traveling to the left. . If at each time step, we add these two . waves together at every point in space, we obtain a wave that doesn't move. Even though the amplitude changes in time, the location of those amplitude shifts do not. It is a standing wave. A standing wave is thus distinguished by waves in which the position of the nodes remains fixed at all times. Standing waves arise if the space in which the waves can propagate is bounded.

Decreasing Energy

Increasing Wavelength

Electromagnetic Radiation consists of visible light, ultraviolet radiation, infrared radiation, gamma rays, Xrays, radio waves, etc. This type of wave involves periodic oscillations in electrical and magnetic fields.

Chem 6A - Chapter 7

Interaction of an electric field with an oscillating dipole moment: The two interact if the frequency and phase are the same.

Chem 6A - Chapter 7

Constructive Interference

Destructive Interference

When parallel rays of light of wavelength ! are incident on a slit of width a, diffraction occurs due to constructive & destructive interference. The extent of interference depends on the angle that the light waves emerge at. In (a) above, constructive interference is maximize, while in (b), destructive interference occurs, resulting in a minimum. In (c), every other wave is out of phase, resulting in primarily destructively interference, and a near minimum.

When parallel rays of light of wavelength ! are incident on a slit of width a, diffraction occurs due to constructive & destructive interference. The extent of interference depends on the angle that the light waves emerge at. Destructive interference is maximized by the equation given above. If no interference (diffraction) occurs, a simple square wave intensity profile would be observed.

Chem 6A - Chapter 7

Constructive and destructive interference upon light waves coming from two point sources (left), or equivalently, upon emerging from two slits (above). Constructive interference results in maxima (red or bright spots to left) and destructive interference results in minima (black or dark spots to left).

single slit results double slit results

A particle going through one slit displays wave-like behavior, as a diffraction pattern is observed. Particle behavior is observed in that exactly half of the electrons strike each slit when one is closed. Having both slits open changes the measurement, and a diffraction pattern is observed, indicating each particle goes through BOTH SLITS. Behavior as both a wave and a particle is a fundamental aspect of the microscopic world described by quantum mechanics.

Chem 6A - Chapter 7

Hertz (1887): showed that when a metal is irradiated with UV light, an electron may be ejected.

"!

Experimental Observations: #! No electrons were ejected below a certain (metal-specific) cut-off or threshold frequency (!0). #! For light of frequency ! > !0, the kinetic energy of the ejected electron was directly proportional to the frequency ! but independent of the light intensity. #! The number of ejected electrons depends on the light intensity. #! Even at arbitrarily low light intensity, electrons are ejected immediately if the frequency ! exceeds the threshold frequency (!0).

"!

Einsteins Explanation (1905): #! Light of frequency ! is composed of particles (now referred to as photons), each of energy E = h!. #! The intensity of the light is proportional to the number of photons. #! Each metal has a characteristic minimum threshold energy (work function, ") required to remove an electron (determined by bonding in the metal, but similar to an ionization energy). #! The kinetic energy of the ejected electron is the photon energy minus the work function (threshold energy). 1 KE = mv 2 = h! " # = h! " h!

Slope = h

Threshold = "o

0

Chem 6A - Chapter 7

Einstein showed that the energy of light is proportion to its frequency and that h is a universal constant. The photoelectric effect demonstrates that light (photons) displays particle-like behavior

1 KE = mv 2 = h! " # = h! " h! 0 2

When h" > #, electrons with energy mv2/2 are ejected.

Each electron ejected by one photon

De Broglies Postulate (1924): Building upon Einsteins result that light could display particle-like behavior, de Broglie hypothesized that one can associate a wave of wavelength ! with a particle moving at momentum p according to the de Broglie Relationship: Wave-like behavior of particles is only observed for very small masses and low velocities (e.g. an electron in an atom) where the wavelength ! is sufficiently large to be observable. It is irrelevant for macroscopic objects. Davisson Germer Experiment (1925): Scattering of an electron beam from a NiO crystal surface demonstrated a variation of scattering intensity characteristic of a diffraction experiment in which waves interfere constructively and destructively, depending upon direction.

Chem 6A - Chapter 7

X-ray Diffraction of Aluminum Photons behave like waves, exhibiting constructive and destructive interference.

Particles (matter) behaves as if it moves in a wave. These matter waves depend on size (mass) & speed:

!baseball =

h = mv

# 6.626 x10"34 kg m2 s "1 & # mile & # ft & # in & # 100 cm & # 3600 s & % (% (% (% (% (% ( $ (142 x10-3 kg )(90 mph) ' $ 5280 ft ' $ 12 in ' $ 2.54 cm ' $ m ' $ hr '

Chem 6A - Chapter 7

Light emitted or absorbed by atoms or molecules appears at certain discrete wavelengths. Rydberg fit emission spectra for H atoms to the following:

Chem 6A - Chapter 7

10

RH = Rydberg constant:

The energy levels for the hydrogen atom are quantized. An electron bound to hydrogen can absorb a photon if the energy (wavelength) is correct and move to a higher energy level. Conversely, an electron can emit a photon and move to a lower energy level. However, the electron cannot be bound to hydrogen and in a state other than the allowed quantized energy states (i.e. the stationary states shown for n = 1, 2, 3, $).

Chem 6A - Chapter 7

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PROBLEM:

A hydrogen atom absorbs a photon of visible light and its electron enters the n = 4 energy level. Calculate (a) the change in energy of the atom and (b) the wavelength (in nm) of the photon. (a) The H atom absorbs visible light, so the electron is going from n = 2 to n = 4. Calculate %E. (b) Use %E = h! = hc / $ to find $."

PLAN:

SOLUTION: (a)

(b )

Plancks Quantum Hypothesis: Radiators (energy sources) exist only in certain allowed energy levels, and radiate only in certain integer multiples of a basic energy unit ( a quanta of h!, with n = 0, 1, 2, 3, $). Einsteins Quantum Hypothesis: Photons are spatially localized packets of light whose energy is proportion to its frequency.

De Broglie Postulate / Wavelength: Particles show wave-like behavior too. Line Spectra of Atoms: Atoms & Molecules have discrete energy levels, and emit or absorb energy at discrete wavelengths.

Quantization of Energy

Chem 6A - Chapter 7

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Wave motion in restricted systems: A.! Waves on a string are similar to a particle confined to a small region (the so called one dimensional particle in a box). B.! Circular waves are similar to a confined particle on a ring, and mimics molecular rotational motion (in 2-D) or electron motion around the nucleus.

ml = integer

ml % integer

Chem 6A - Chapter 7

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"!

Classical mechanics: particles have trajectories and can precisely be described according to location (x) and linear momentum (p) In quantum mechanics we talk about probability: waves are spread out as they oscillate Wave-Particle Duality denies the ability of knowing the trajectory of particles (complementarity) Heisenberg Uncertainty principle:

"!

"!

"!

"!

A sine wave of wavelength ! implies that the momentum p is precisely known (using the de Broglie relationship). But the wavefunction and the probability density &*& is spread over all space. Hence p is exact (precisely known), and the position x is unknown. Adding together several waves of different wavelength (a linear combination) will produce an interference pattern (a superposition) which begins to localize the wave!

Hence, there is an inherent increase in the uncertainty in 'p as the position becomes more localized (i.e. 'x decreases).

However, this localization in position results in a spreading of the momentum values since each wave added has a different momentum.

Chem 6A - Chapter 7

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A quantum mechanical system is completely specified by a wavefunction & = &(x,y,z,t). The wavefunction contains all the information there is to know about the system. An operator "operates" upon a function and produces another function. For every operator, there is a collection of functions which, when operated on by the operator, produces THE SAME function, modified only by a constant factor. Such a function is called an eigenfunction of that operator and the constant factor is called the eigenvalue of that eigenfunction.

Quantum mechanics involve eigenvalue equations. Any observable property of a system (energy, momentum, angular momentum, dipole moment, etc.) has its own operator. The eigenfunctions are the wavefunctions of the system and the eigenvalues are the values of the property - the number that we measure. The Hamiltonian is the energy operator for the system and the Schrdinger equation is an eigenvalue equation.

! n ( x) = E n! n ( x) H

"!

"!

We can exactly solve the Schrodinger Equation for simple cases. The particle in a box solution:

x=0

x=L

"!

Since n is an integer, E is quantized with discrete values of E with E > 0!

Chem 6A - Chapter 7

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n=4

Eigenfunctions

Probability Density

n=2 n=1

! n ( x) =

2 n" x sin ; n = 1, 2, L L

!* ( x) ! n ( x) = n

2 2 n" x sin L L

E/(h2/8mL2)

The allowed energy levels for a particle in a box. Note that the energy levels increase as n2, and that their separation increases as the quantum number increases.

Chem 6A - Chapter 7

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Where V(x,y,z) = 0 inside the box, and V(x,y,z) = ( outside the box. Outside the 3-D box, &(x,y,z) = 0, and inside the box:

!n

x , n y , nz

( x, y, z ) =

The energy is quantized with 3 quantum numbers: nx, ny, nz. The lowest energy state has all quantum numbers equal to one. This is called the ground-state energy or zero-point energy:

For the case of a cubic box (Lx = Ly= Lz), the energy is:

Panel A & B: Plots of the Probability Density (&*&) for the 1s Orbital. It is greatest at the nucleus and spherically symmetric, decreasing as one moves out from the nucleus. Panel C & D: Plots of the Radial Distribution Function for the 1s Orbital. This is the probability that the electron will be found anywhere in a shell of radius r. It is equal to zero at the nucleus, maximizes at the Bohr radius, and decreases as one moves out further from the center. It too is spherically symmetric. Panel E: A contour plot of the 1s Orbital showing the volume where the electron spends 90% of its time.

Chem 6A - Chapter 7

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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.

2s Orbital

1s Orbital

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

Chem 6A - Chapter 7

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An atomic orbital is specified by three quantum numbers: n the principal quantum number - a positive integer ( 1, 2, 3, $$) l the angular momentum quantum number - an integer from 0 to (n - 1) ml the magnetic moment quantum number - an integer from l to +l

The organization of orbitals into shells (characterized by n) and subshells (characterized by I).

The energy levels of the hydrogen atom showing the subshells and (in square brackets) the numbers of orbitals in each subshell. In hydrogenic atoms, all orbitals of a given shell have the same energy.

Chem 6A - Chapter 7

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Chem 6A - Chapter 7

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Hydrogen Atom Hamiltonian

We seek solutions then of the form:

Chem 6A - Chapter 7

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(3) It is further required that the quantum number l in the total solution satises l < n-1. Thus, we have the following form for the wavefunction, and three quantum numbers:! Principle quantum number: radial part angular part Angular momentum quantum number: Magnetic quantum number:

Normalization constant Term to make all wavefunctions go to zero at the nucleus except for l=0

Decaying exponential in r

Hydrogen Wavefunctions

Angle independent!

Chem 6A - Chapter 7

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2p orbitals

Chem 6A - Chapter 7

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The 3d orbitals

Chem 6A - Chapter 7

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PROBLEM: What values of the angular momentum (l) and magnetic (ml) quantum numbers are allowed for a principal quantum number (n) of 3? How many orbitals exist for n = 3? PLAN: Follow the rules for allowable quantum numbers found in the text. l values can be integers from 0 to (n 1); ml can be integers from -l through 0 to +l. SOLUTION: For n = 3, l = 0, 1, 2 For l = 0, ml = 0 For l = 1, ml = -1, 0, +1 For l = 2, ml = -2, -1, 0, +1, +2 There are 9 ml values and therefore, 9 orbitals with n = 3.

PROBLEM: Give the name, magnetic quantum numbers, and number of orbitals for each sublevel with the following quantum numbers: (a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l = 3

PLAN: Combine the n value and l designation to name the sublevel. Knowing l, we can find ml and the number of orbitals. SOLUTION: n (a) (b) (c) (d) 3 2 5 4 l 2 0 1 3 sublevel name 3d 2s 5p 4f possible ml values -2, -1, 0, +1, +2 0 -1, 0, +1 -3, -2, -1, 0, +1, +2, +3

# of orbitals 5 1 3 7

Chem 6A - Chapter 7

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