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Classical Mechanics

-studies motion and behavior of objects on a bigger scale, predicts a precise trajectory for particles,allows

translational,vibrational and rotational to be excited

Classical physics: light-electromagnetic radiation

Quantum Mechanics-behavior of sub-atomic particles

Electromagnetic field

An oscillating electric and magnetic disturbance that spreads as a harmonic wave through empty space, the vacuum.

Has two components: Electric Field & Magnetic Field

*The wave travels at a constant speed called the speed of light, c, which is about 3 108 m s1

Wavelength is the distance bet the neighboring peaks of the curves

Frequency (v) - # of times per second at which its displacement at fixed point return to its original value

# of cycle a wave complete its one second

Measured in Hertz: 1 Hz= 1 s-1

*Wavelength is inversely proportional to frequency but directly proportional to velocity

Wave number- spatial wavelength, inversely proportional to the wavelength, usually in cm-1

V = frequency (Hz)

= wavelength (cm)

= wavelength (cm)

Electromagnetic Spectrum- description and classification of electromagnetic field according to its frequency and wavelength

-states that energy is emitted or absorbed in a discrete units called quanta

-E=hv where h=Plancks constant 6.63X10-34 Js where: v=frequency, E=electromagnetic wave

-energy is emitted or absorbed as a whole number of multiple of h (2h, 3h,..)

Karl Ernst Ludwig and Marx Planck-Father of Quantum Theory

Planck-energy of light is proportional to the frequency

Albert Einstein-determine that light exist in discrete quanta of energy or photons

Blackbody- name given to a theoretical ideal matter, object capable of emitting or absorbing wavelength of radiation equally

ENERGY DISTRIBUTION

-energy density increases in shorter wavelengths as the temp is raise, and the peak shifts to a shorter wavelength

-total energy density increases as the temp is increased

BLACK BODY RADIATION

-type of electromagnetic radiation within or surrounding a body in thermodynamic equilibrium with its environment or

emitted by a black body at constant uniform temp

Lord Rayleigh- electromagnetic radiation as a collection of oscillators for all possible frequencies

Ultraviolet Catastrophe- large amount of energy is radiated in high frequency region

Rayleigh-Jeans Law- infinite energy density at short wavelengths. This approach to infinity is Ultraviolet Catastrophe

dE = energy density

k = Boltzmanns constant (k = 1.381 x 10-23 J/K)

Planck distribution- fits the experimental curve very well at wavelengths

k = Boltzmanns constant (k = 1.381 x 10-23 J/K).

h = Plancks constant (h = 6.626 x 10-34 Js.)

DULONG AND PETIT LAW

-Pierre-Louis Dulong and Alexis Therese Petit- determined the number of heat capacities of monatomic

solids

(25 J/ mol K)

-significant deviations from their law was observed when advances in refrigeration techniques made it

possible to measure heat capacities at low temperature

Where R is the gas constant

Einstein Formula

Einstein Temperature

-expressing frequencies of oscillation of atoms as a temperature

-high frequency corresponds to high Einstein temperature

Debye Formula

Physical Chemistry 2

Debye Temperature- they oscillate over a range of frequencies from 0 up to maximum value

Classical Mechanics- work done in the areas of physics and chemistry, study of motion of bodies,

Also called Newtonian Mechanics

Classical physics- predicts precise trajectory for particles

-allows translational, rotational, vibrational to be excited

Quantum Mechanics-occur at atomic scale, behavior of matter and light on atomic and sub-atomic particle

Quantum-Latin word which means Bundle

*Therefore, we are studying the motion of objects that come in small bundles called quanta.

Timeline of Quantum Mechanics

1859

- Kirchhoff introduces the concept of a blackbody and proves that its emission spectrum depends only on its temperature.

1860-1900

- Ludwig Eduard Boltzmann, James Clerk Maxwell and others develop the theory of statistical mechanics.

Boltzmann argues that entropy is a measure of disorder.

1887

- Heinrich Hertz discovers the photoelectric effect, shown by Einstein in 1905 to involve quanta of light.

1888

- Johannes Rydberg modifies the Balmer formula to include all spectral series of lines for the hydrogen atom, producing

the Rydberg formula which is employed later by Niels Bohr and others to verify Bohr's first quantum model of the atom.

1895

- Wilhelm Conrad Rntgen discovers X-rays in experiments with electron beams in plasma.

1896

- Antoine Henri Becquerel accidentally discovers radioactivity while investigating the work of Wilhelm Conrad Rntgen; he

finds that uranium salts emit radiation that resembled Rntgen's X-rays in their penetrating power. In one experiment,

Becquerel wraps a sample of a phosphorescent substance, potassium uranyl sulfate, in photographic plates surrounded

by very thick black paper in preparation for an experiment with bright sunlight; then, to his surprise, the photographic

plates are already exposed before the experiment starts, showing a projected image of his sample

1900

1905

- Max Planck explains blackbody radiation in the context of quantized energy emission: Quantum theory is born.

- Albert Einstein proposes that light, which has wavelike properties, also consists of discrete, quantized bundles of energy,

which are later called photons.

1911

- Ernest Rutherford proposes the nuclear model of the atom.

1913

- Niels Bohr proposes his planetary model of the atom, along with the concept of stationary energy states, and accounts

for the spectrum of hydrogen.

1914

- James Franck and Gustav Hertz confirm the existence of stationary states through an electron-scattering experiment.

1923

- Louis de Broglie generalizes wave-particle duality by suggesting that particles of matter are also wavelike.

1924

- Satyendra Nath Bose and Albert Einstein find a new way to count quantum particles, later called Bose-Einstein statistics,

and they predict that extremely cold atoms should condense into a single quantum state, later known as a Bose-Einstein

condensate.

1925

- Wolfgang Pauli enunciates the exclusion principle.

Werner Heisenberg, Max Born, and Pascual Jordan develop matrix mechanics, the first version of quantum

mechanics, and make an initial step toward quantum field theory.

1926

- Erwin Schrdinger develops a second description of quantum physics, called wave mechanics. It includes what

becomes one of the most famous formulas of science, which is later known as the Schrdinger equation.

- Enrico Fermi and Paul A.M. Dirac find that quantum mechanics requires a second way to count particles, Fermi-Dirac

statistics, opening the way to solid-state physics.

- Dirac publishes a seminal paper on the quantum theory of light.

1927

- Heisenberg states his Uncertainty Principle, that it is impossible to exactly measure the position and momentum of a

particle at the same time.

1928

- Dirac presents a relativistic theory of the electron that includes the prediction of antimatter

1932

- Carl David Anderson discovers antimatter, an antielectron called the positron.

1948

- Richard Feynman, Julian Schwinger, and Sin-Itiro Tomonaga develop the first complete theory of the interaction of

photons and electrons, quantum electrodynamics, which accounts for the discrepancies in the Dirac theory.

1957

- John Bardeen, Leon Cooper, and J. Robert Schrieffer show that electrons can form pairs whose quantum properties

allow them to travel without resistance, providing an explanation for the zero electrical resistance of superconductors. This

theory was later termed the BCS theory (after the surname initials of the three physicists).

1959

- Yakir Aharonov and David Bohm predict that a magnetic field affects the quantum properties of an electron in a way that

is forbidden by classical physics. The Aharonov-Bohm effect is observed in 1960 and hints at a wealth of unexpected

macroscopic effects.

1960

- Building on work by Charles Townes, Arthur Schawlow, and others, Theodore Maiman builds the first practical laser.

1964

- John S. Bell proposes an experimental test, "Bell's inequalities," of whether quantum mechanics provides the most

complete possible description of a system.

1970

- Foundations are laid for the standard model of particle physics, in which matter is said to be built

of quarks and leptons that interact via the four physical forces.

1982

- Alain Aspect carries out an experimental test of Bell's inequalities and confirms the completeness of quantum

mechanics.

1991 - Richard R. Ernst develops two-dimensional nuclear magnetic resonance spectroscopy (2D-FT NMRS) for small molecules in

solution and is awarded the Nobel Prize in Chemistry in 1991 "for his contributions to the development of the methodology

of high resolution nuclear magnetic resonance (NMR) spectroscopy."

2000

- Scientists at European Organization for Nuclear Research (CERN) publish experimental results in which they claim to

have observed indirect evidence of the existence of a quarkgluon plasma, which they call a "new state of matter.

2009 - Aaron D. O'Connell invents the first quantum machine, applying quantum mechanics to a macroscopic object just large

enough to be seen by the naked eye, which is able to vibrate a small amount and large amount simultaneously.

2014 - Scientists transfer data by quantum teleportation over a distance of 10 feet with zero percent error rate, a vital step towards a

quantum internet.

ELECTROMAGNETIC RADIATION

-produced by oscillating electric and magnetic disturbances

-electric and magnetic fields come at right angles and the combined wave moves perpendicular

James Clerk Maxwell

-first to predict the existence of electromagnetic waves

-proposed that a light-including various forms of radiant energy-is an electromagnetic distribution in the form of waves

-proposed a unified theory of electromagnetism

Physical Chemistry 2

Electromagnetism- how electrically charged particles interact with each other and with magnetic fields

Electromagnetic theory

There are four main electromagnetic interactions:

1. The force of attraction or repulsion between electric charges is inversely proportional to the square of the

distance between them.

2. Magnetic poles come in pairs that attract and repel each other, much as electric charges do.

3. An electric current in a wire produces a magnetic field whose direction depends on the direction of the current.

4. A moving electric field produces a magnetic field, and vice versa.

Heinrich Hertz

-provide an experimental confirmation of Maxwells prediction by producing the first man-made electromagnetic waves

General Properties of all electromagnetic radiation:

Electromagnetic radiation can travel through empty space.

The speed of light is always a constant. (Speed of light : 2.99792458 x 108 m/s)

Wavelengths are measured between the distances of either crests or troughs.

Electromagnetic wave- is the radiation consisting of waves, of energy associated with electric and magnetic fields, resulting from the

acceleration of an electric charge

Properties of Electromagnetic Waves

1. The energy of electromagnetic radiation is directly proportional to the frequency.

2. Electromagnetic radiation with higher frequency than visible light has higher energy. This is why ultraviolet light can burn

your skin and X-rays and gamma rays can damage tissues.

3. Electromagnetic radiation with a lower frequency than visible light has less energy

4. Higher frequency electromagnetic waves have shorter wavelengths

5. Wavelengths vary greatly from long wavelengths (many meters) to very short wavelengths (the size of atomic nuclei).

Electromagnetic spectrum- number of different radiations.

Radiation is energy that travels and spreads out as it goes.

Radio waves

the lowest frequency which is about 30 billion hertz, or 30 gigahertz (GHz),

longest wavelength greater than about 10 millimeters (0.4 inches),

Ionosphere is a set of ionized layers in the upper portions of the atmosphere

Radio pulses travel more slowly within the ionosphere than in free space,

Radio is used primarily for communications including voice, data and entertainment media.

Microwaves

fall in the range of the EM spectrum between radio and IR

used for high-bandwidth communications, radar and as a heat source for microwave ovens and industrial applications.

Infrared

Infrared is in the range of the EM spectrum between microwaves and visible light.

IR light is invisible to human eyes, but we can feel it as heat if the intensity is sufficient.

Visible light

found in the middle of the EM spectrum, between IR and UV.

visible to most human eyes.

Ultraviolet

Ultraviolet light is in the range of the EM spectrum between visible light and X-rays

UV light is a component of sunlight; however, it is invisible to the human eye.

It has numerous medical and industrial applications, but it can damage living tissue.

X-rays

Soft X-rays comprise the range of the EM spectrum between UV and gamma rays.

Hard X-rays occupy the same region of the EM spectrum as gamma rays.

The only difference between them is their source: X-rays are produced by accelerating electrons, while gamma rays are

produced by atomic nuclei.

Gamma-rays

range of the spectrum above soft X-rays.

Gamma radiation causes damage to living tissue, which makes it useful for killing cancer cells

BOHR ATOMIC THEORY

A.

BOHR ATOMIC MODEL

An atom is made up of three particles, electrons, protons and neutrons. Electrons have a negative charge and protons

have a positive charge whereas neutrons have no charge. They are neutral. Due to the presence of equal number of negative

electrons and positive protons, the atom as a whole is electrically neutral.

The protons and electrons are located in a small nucleus at the centre of the atom. Due to the presence of protons, the

nucleus is positively charged.

The electrons revolve rapidly around the nucleus in fixed circular paths called energy levels or shells. The 'energy

levels' or 'shells' or 'orbits' are represented in two ways: either by the numbers 1, 2, 3, 4, 5 and 6 or by letters K, L, M, N, O and

P. The energy levels are counted from centre outwards.

Each energy level is associated with a fixed amount of energy. The shell nearest to the nucleus has minimum energy

and the shell farthest from the nucleus has maximum energy.

There is no change in the energy of electrons as long as they keep revolving with the same energy level. But, when an electron

jumps from a lower energy level to a higher one, some energy is absorbed while some energy is emitted.

When an electron jumps from a higher energy level to a lower one, the amount of energy absorbed or emitted is given

by the difference of energies associated with the two levels. Thus, if an electron jumps from orbit 1 (energy E 1) to orbit 2 (energy

E2), the change in energy is given by E2 - E1.

The energy change is accompanied by absorption of radiation energy of E = E 2 E1 = h where, h is a constant

called 'Planck's constant' and is the frequency of radiation absorbed or emitted. The value of h is 6.626 x 10 -34 J-s. The

absorption and emission of light due to electron jumps are measured by use of spectrometers.

B.

Physical Chemistry 2

Electrons revolve round the nucleus with definite velocities in concentric circular orbits situated at definite distances

from the nucleus. The energy of an electron in a certain orbit remains constant. As long as it remains in that orbit, it neither emits

nor absorbs energy. These are termed stationary states or main energy states.

Bohr proposed that the angular momentum of an electron is quantized. Thus, the motion of an electron is restricted to

those orbits where its angular momentum is an integral multiple of h/2, where h is Plancks constant.

Thus we have the relationship mvr = nh/2, where m is mass of electron, v is velocity of electron of said orbit, r is radius

of that orbit, n is a simple integer.

The stationary states or allowed energy levels are only those where n = 1, 2, 3. This is called Bohr quantum condition.

The energy of an electron changes only when it moves from one orbit to another. An electronic transition from an inner

orbit to outer orbit involves absorption of energy. Similarly, when an electron jumps from an outer orbit to inner orbit it releases

energy, which is equal to the difference between the two energy levels.

Based on the Bohr theory, Bohr calculated the radii of the various orbits and the energies associated with the electrons

present in those shells.

Heisenbergs Uncertainty Principle

-quantum theory proposed that energy was not continuous but instead came in discrete packets (quanta) and that light

could be described as both a wave and a stream of these quanta.

uncertainty principle also called the Heisenberg Uncertainty Principle, or Indeterminacy Principle

says that the position and the velocity of an object cannot both be measured exactly, at the same time, even in theory.

exact position and exact velocity together have no meaning in nature.

For example, you can measure the location of an electron, but not its momentum (energy) at the same time.

It is a statement of the effects of wave-particle duality on the properties of subatomic objects.

product of the uncertainties in position and velocity is equal to or greater than a tiny physical quantity, or constant (about

10-34 joule-second, the value of the quantity h (where h is Planck's constant). Only for the exceedingly small masses of atoms and

subatomic particles does the product of the uncertainties become significant.

Particle Confinement

The more intense the undulations of the associated wave become, however, the more ill-defined becomes the

wavelength, which in turn determines the momentum of the particle. So a strictly localized wave has an indeterminate wavelength;

its associated particle, while having a definite position, has no certain velocity.

A particle wave having a well-defined wavelength, on the other hand, is spread out; the associated particle, while having a

rather precise velocity, may be almost anywhere. A quite accurate measurement of one observable involves a relatively large

uncertainty in the measurement of the other.

The uncertainty principle is alternatively expressed in terms of a particle's momentum and position.

The momentum of a particle is equal to the product of its mass times its velocity. Thus, the product of the uncertainties in

the momentum and the position of a particle equals h/(2) or more. The principle applies to other related (conjugate) pairs of

observables, such as energy and time: the product of the uncertainty in an energy measurement and the uncertainty in the time

interval during which the measurement is made also equals h/(2) or more.

Therefore, the uncertainty principle, that certain quantity, such as position, energy and time, are unknown, except by

probabilities. In its purest form, the uncertainty principle states that accurate knowledge of complementarily pairs is impossible.

Quantum Mechanical Postulates

I.

Postulate 1: wavefunction attempts to describe a quantum mechanical entity (photon, electron, x-ray, etc.) through

its spatial location and time dependence.

The state of a quantum mechanical system is completely specified by the wavefunction (x; t).

The Probability that a particle will be found at time t0 in a spatial interval of width dx centered about x0 is determined by

the wave function as:

P(x0, t0) dx = * (x0, t0) (x0, t0) dx = |(x0, t0)|2 dx

In order for (x, t) to represent a viable physical state, certain conditions are required:

1. The wave function must be a single-valued function of the spatial coordinates. (single probability for being in a

given spatial interval)

2. The first derivative of the wave function must be continuous so that the second derivative exists in order to

satisfy the Schrdinger equation.

3. The wave function cannot have infinite amplitude over a finite interval. This would preclude normalization over

the interval.

II.

Postulate 2: For every measurable property of the system in classical mechanics such as position, momentum, and

energy, there exists a corresponding operator in quantum mechanics.

Quantum mechanical operators are classified as Hermitian operators as they are analogs of Hermitian matrices that

are defined as having only real eigenvalues. Also, the eigenfunctions of Hermitian operators are orthogonal.

List of Chemical Observables and Q.M. Operator

Operators act on a wave function from the left, and the order of operations is important (much as in the case of multiplying by

matrices - commutatively is important).

Physical Chemistry 2

III.

Individual Measurements

Postulate 3: For a single measurement of an observable corresponding to a quantum mechanical operator, only values

that are eigenvalues of the operator will be measured.

If measuring energy: one obtains eigenvalues of the time-independent Schrdinger equation:

n (x,t) = Enn(x,t)

Note: The total wave function defining a given state of a particle need not be an eigenfunction of the operator (but one

can expand the wave function in terms of the eigenfunctions of the operator as a complete basis).

IV.

Postulate 4: The average, or expectation, value of an observable corresponding to a quantum mechanical operator

is given by:

<a>=

This is a general form for the expectation value expression. If the wavefunction is normalized, then the denominator

is identically 1 (this is assumed to be the case since every valid wavefunction must be normalized).

Consider the following cases:

A. The wavefunction represents an eigenfuntion of the operator of interest. The expectation value of a

measurable is:

<a> =

= aj

B.

Now consider that the wavefunction itself is not an eigenfunction of the operator . However, since the

wavefunction belongs to the space of functions that are eigenfunctions of the operator, we can construct

(expand) the wavefunction from the basis of eigenfunctions of . Thus:

(x,t) = bnn (x,t)

Where the bnn (x,t) are eigenfunctions of the operator . Consider:

<a> =

=

=

=

The only terms that survive m =n terms (orthogonality of eigenfunctions of Hermitian operators). Thus,

<a> =

=

The average value of the observable is a weighted average of the possible eigenvalues (i.e., possible measurement

outcomes).The weighting factor is the square of the expansion coefficient, bn for the n'th eigenfunction with eigenvalue an.

Thus, the expansion coefficients, bn represent the degree to which the full wavefunction possesses the character of

the eigenfunction n. By anology to vector space, the coefficients can be thought of as projections of the wavefunction on to the

basis functions (i.e., the eigenfunctions of the operator).

Identically prepared quantum systems can have different outcomes with regard to measure observables. (super

position of states)

Initial measurement of a quantum mechanical system is probabilistic. Subsequent measurements will yield the same

value of the observable. This is a transition from a probabilistic to a deterministic outcome. Collapse of the wavefunction.

V.

Time Evolution

Postulate 5: The time-dependent Schrdinger equation governs the time evolution of a quantum mechanical system:

(x,t) =

The Hamiltonian operator contains the kinetic and potential operators. This equation reflects the deterministic

(Newtonian) nature of particles/waves. It appears to be in contrast to Postulate 4 (many observations lead to different

measured observables, each weighted differently, i.e., a probabilistic view of the particle/wave). The reconciliation is in the fact

that Postulate 4 pertains to the outcomes of measurements at 5 a specific instant in time.

Postulate 5 allows us to propagate the wavefunction in time (we propagate a probabilistic entity). Then, at some

future time, if we make another measurement, we are again faced with the implications of Postulate 4.

In dealing stationary quantum mechanical states, we do not need to have an explicit knowledge of the time

dependent wavefunction, particularly if the operator of interest is independent of time. Consider:

(x) n (x,t) = ann (x,t)

Recalling that the time dependent wavefunction can be written as the product of time-independent and timedependent components:

n (x,t) = n (x)

Thus:

Physical Chemistry 2

(x) n

(x) n (x) =

ann (x)

Thus, for time-independent operators, the eigenvalue equations for n(x) are to be considered.

Free Particle

-the simplest system in quantum mechanics

-has potential energy V=0 everywhere

-is called a free particle since it has no forces acting on it.

We consider the one-dimensional case, with motion only in the x direction, giving the Schrodinger equation:

Simplifying, the Free Quantum Particle Total Energy is

There is no restriction on the value of k. Thus a free particle, even in quantum mechanics, can have any non-negative

value of the energy and the energy spectrum is continuous.

Particle in 1D Box

This is the simplest non-trivial application of the Schrdinger equation, but one which illustrates many of the fundamental

concepts of quantum mechanics. For a particle moving in one dimension (again along the x- axis), the Schrdinger equation can be

written

These are the only values of the energy which allows solutions of the Schrdinger

equation consistent with the boundary conditions. The integer n, called a quantum

number, is appended as a subscript on E to label the allowed energy levels. The

normalized eigenfunctions is

Inside box, similar to infinite box

Outside box decays ( x ) exponentially

- ( x ) decays most rapidly for energy eigenvalues near bottom of box

-Nonzero wave function in classically forbidden region

-Finite number of bound

Particle in a Three-Dimensional Box

A real box has three dimensions. Consider a particle which can move freely with in

rectangular box of dimensions a x b x c with impenetrable walls.

Inside the box, where the potential energy is everywhere zero, the Hamiltonian is

simply the three-dimensional kinetic energy operator and the Schrdinger equation reads

The normalized solutions X(x), Y (y), Z(z) can therefore be written down as

Three quantum numbers are required to specify the state of the three-dimensional system. The corresponding eigenfunctions are

Physical Chemistry 2

State- Unique wave function

Degeneracy- The number of states that have the same energy

Free-Electron Model

The simple quantum-mechanical problem we have just solved can provide an instructive application to chemistry:

the free-electron model (FEM) for delocalized -electrons.

Example Problem for electrons in conjugated molecules

What is the length of delocalization or network with an experimental maximum wavelegth of 375 nm?

For Experimental box length, Use

SOLUTION:

Until 1925, all attempts to deal with atomic and molecular structural problems were based on classical mechanics, in

which the structural units of the atom were treated as particles with determined momenta and positions upon which were

superimposed postulated quantized conditions such as those of Bohr. In 1925-1926, Werner Heisenberg and Erwin Schrdinger

independently propped a new quantum or wave mechanics which takes cognizance of the wave and particle duality of matter and

which deals with atomic and molecular scale problems in a totally different manner. Erwin Schrdinger was an Austrian theoretical

physicist who achieved fame for his contributions to quantum mechanics. Schrdinger equation, which he formulated in 1926 to

describe the quantum state of a system, is his most enduring achievement at a more technical level. Also, he produced the papers

that gave the foundations of quantum wave mechanics. In those papers he described his partial differential equation that is the

basic equation of quantum mechanics and bears the same relation to the mechanics of the atom as Newtons equations of motion

bear to planetary astronomy.

Adopting a proposal made by Louis de Broglie in 1924 that particles of matter have a dual nature and in some situations

act like waves, Schrdinger introduced a theory describing the behavior of such a system by a wave equation that is now known as

the Schrdinger equation. The solutions to Schrdingers equation, unlike the solutions to Newtons equations, are wave functions

that can only be related to the probable occurrence of physical events. The definite and readily visualized sequence of events of the

planetary orbits of Newton is, in quantum mechanics, replaced by the more abstract notion of probability.

The basis for handling all problems by wave mechanics is the Schrodinger equation. This equation cannot be derived

from the first principles or basic postulates. Rather, it is arrived at in a manner to be described below, and the assumption is then

made that this equation is valid for the treatment of all types of problems which involve atomic and molecular behavior.

Consider a system, such a string, vibrating with a frequency v and producing a wave traveling in the x direction with a

velocity ux and amplitude (height of wave) . For such a system classical mechanics tells us that (Eq. 25)

Where t is the time necessary for the wave to reach a position x. The solution of this equation can be obtained in the form

(Eq. 26)

Where f1(x) is a function only of x and f2(t) can be written as (Eq. 27)

If we differentiate

Physical Chemistry 2

And hence on substitution of Eq. (29) and Eq. (30) into Eq. (25) we get (Eq. 31)

But wave length =ux/v. Making this substitution, (Eq. 31) becomes (Eq. 32)

Equation (32) applies to a wave moving in the x direction only. If we consider a wave moving in three dimensions, then

f1(x) can be replaced by , where = (x,y,z), and Eq.(32) is transformed to Eq.(33)

Or Eq. (34)

Again according to de Broglies hypothesis a wave of length can be considered to be a particle of mass m moving with a

velocity v, namely = h/mv . Substituting the latter into Eq. (34), we obtain Eq. (36)

Finally, the total energy of the particle, E, is the sum of its potential energy, U, and its kinetic energy Ek = (1/2) mv2.

Consequently,

And

Substitution of the latter expression to Eq. (36) thus yields Eq. (37)

which is the Schrodingers wave equation, and the postulated basis of all quantum mechanical behavior of matter.

TIME-INDEPENDENT SCHRODINGER EQUATION

Where:

V(x) = the potential energy of the particle at the point x

E = sum of potential and kinetic energies

= convenient modification of Plancks constant

Physical Chemistry 2

Js

In general case, Schrodinger equation is written

Where is the Hamiltonian operator for the system:

For the evolution of a system with time, it is necessary to solve the time-dependent Schrodinger equation:

Although the Schrodinger equation should be regarded as a postulate, like Newtons equations of motion, it can be seen

to be plausible by noting that it implies the de Broglie relation for a freely moving particle in a region with constant potential energy

V:

General strategies for solving differential equations of this and other types that occur frequently in physical chemistry, we

note that a solution is:

Where

In quantum mechanics, a wave function that describes the spatial distribution of a particle (a spatial wave function) is

complex if the particle it describes has a net motion. In the present case, we can use the relation

to

write

.

The real and imaginary parts of can be shown as

Source: Atkins

and we see that the imaginary component

real and imaginary parts of the wave function are real, in the sense of being present, and we express as a complex function

simply to help the visualization of the motion of the particle the wave function describes.

harmonic wave,

implies that

is a wave of wavelength

). The quantity

Because

, which

it follows that

Therefore, the linear momentum is related to the wavelength of the wave function by

Physical Chemistry 2

APPROXIMATION METHOD

Techniques of Approximation

Many problems and almost all the problems of interest in chemistry do not have exact solutions. To make progress with

these problems we need to develop techniques of approximation.

There are two major approaches:

Variation theory

Perturbation theory

Variation theory

It is one way of finding approximations to the lowest energy eigenstate or ground state, and some excited states. This

allows calculating approximate wave functions such as molecular orbital.

Perturbation theory

The Hamiltonian for the problem we are trying to solve, , can be expressed as the sum of a simple Hamiltonian, (0),

which has known eigenvalues and eigenfunctions, and a contribution, (1), which represents the extent to which the true Hamiltonian

differs from the model Hamiltonian:

= (0) + (1)

Time-independent perturbation theory

Perturbation is always present and unvarying.

It might represent a dip in the potential energy of a particle in a box in some region along the length of the box.

the true energy of the system differs from the energy of the simple system

E = E(0) + E(1) + E(2) + . . .

where E(1) is the first-order correction to the energy, a contribution proportional to (1)E(2) is the second-order correction

to the energy, a contribution proportional to (1)2

The true wave function also differs from the simple wave function

= (0) + (1) + (2) + . . .

(1) is the first-order correction to the wave function

First-order corrections to the energy of the ground state with the wave functions 0 and energy E0

E(1) as the average value of the perturbation

Second-order corrections to the energy of the ground state with the wave function 0 and energy E0

Analogy

shift in energy of vibration of a violin string when small weights are hung along its length

We should note the following three features of Second-order corrections to the energy of the ground state:

1. Because En (0) >E0 (0), all the terms in the denominator are negative and, because the numerators are all positive,

the second-order correction is negative, which represents a lowering of the energy of the ground state.

2. The perturbation appears (as its square) in the numerator; so, the stronger the perturbation, the greater the lowering

of the ground-state energy.

3. If the energy levels of the system are widely spaced, all the denominators are large, so the sum is likely to be small;

in which case the perturbation has little effect on the energy of the system: the system is stiff, and unresponsive to

perturbations. The opposite is true when the energy levels lie close together.

Example 9.5 Using perturbation theory

10

Physical Chemistry 2

Find the first-order correction to the ground-state energy for a particle in a well with a variation in the potential of the form

V = sin(x/L), as in Fig. 9.43.

Method

Identify the first-order perturbation hamiltonian and evaluate E 0(1) from

First-order corrections to the energy of the ground state.

We can expect a small lowering of the energy because the average potential

energy of the particle is lower in the distorted box.

Answer:

The perturbation hamiltonian is

(1) = sin(x/L)

Therefore, the first-order correction to the energy is

The perturbation is either switched on and allowed to rise to its final value

or is varying in time. Many of the perturbations encountered in chemistry are timedependent. The most important is the effect of an oscillating electromagnetic field, which is responsible for spectroscopic transitions

between quantized energy levels in atoms and molecules.

Hamiltonian for the system

= (0) + (1)(t)

(1)(t)is the time-dependent perturbation

(1)(t) = zEcost

Where

E is its amplitude

Note: An electric dipole consists of two electric charges +q and q separated by a distance R. The electric dipole moment

vector has a magnitude = qR.

The rate of change of population of the state f due to transitions from state i, wfi, is proportional to the square

modulus of the matrix element of the perturbation between the two states:

Because in our case the perturbation is that of the interaction of the electromagnetic field with a molecule (eqn 9.67), we

conclude that

Therefore, the rate of transition, and hence the intensity of absorption of the incident radiation, is proportional to the

square of the transition dipole moment:

The size of the transition dipole can be regarded as a measure of the charge redistribution that accompanies a transition.

The rate of transition is also proportional to E2, and therefore the intensity of the incident radiation (because the intensity is

proportional to E2).

Example Problems

(a) Involving Variational Method

Using the variational method approximation, find the ground state energy of a particle in a box using this trial function:

Solution:

The problem asks that we apply variational methods approximation to our trial wavefunction.

11

Physical Chemistry 2

Where

the Schrodinger equation using:

Use the perturbation theory to calculate the first - order corrections to the ground state energy of

a.

b. A quartic oscillator that arises from only using a quartic term cx4 and compare the results.

Solution:

A.) The Hamiltonian for this problem is

12

Physical Chemistry 2

B.)

The

13

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