Inorganic and Physical Chemistry: Lesson 1 Introduction to quantum Theory

Macroscopic vs Microscopic world: In our day -today world, we come across different types of materials: air, water biomass, rocks, living systems, crystalline and amorphous materials, polymers, metals to name a few. All the various materials are defined by measurable physicochemical properties (bulk properties) like mass, volume, specific heats, hydrodynamic properties, hardness , electrical and magnetic properties etc. These properties are measured on the bulk materials. If we look closer, we see drastic differences in the properties of even similar materials : e.g., diamond and graphite; brick and granite; water and hydrogen sulphide; sugar and starch; In order to understand the differences in the properties of substances, one has to go deeper into the understanding of the building blocks a material is made of. Ultimately , one could trace the origin of all physicochemical properties, to the way molecules are arranged in a material- in the way atoms are arranged in molecules-in the way electrons and nuclei are arranged in the molecules. This type of analysis leads us from the macroscopic world to the microscopic world:- i.e., the world of electrons and nuclei and electromagnetic radiation. The of particles in the microscopic world do not obey the Newtons laws of motion. Classical mechanics cannot be applied to describe the motion of electrons in atoms and molecules. Why? Due to the extremely small mass (~10-31 kg) and high velocity (~106ms-1) , the particles can be associated with a wavelength of the order of 10 -10m. This is the order of magnitude of length in atoms and molecules. With such a small mass and high velocity , the motion of these particles is similar to that of wave propagation. It has been proved experimentally, that electrons undergo interference and diffraction similar to photons. The associated wave nature leads to uncertainties in the measurement of certain properties like position, momentum etc., The famous uncertainty relationships postulated by Heisenberg form the basis of new mechanical laws that describe the behavior of electrons and similar particles. Need for quantum theory

The period around 1900 witnessed the dramatic development of new theories, which completely altered the ways of thinking of physicists. Experimental results of far reaching consequences also were obtained during this period. These theories and experiments have completely revolutionized all branches of science. The excitement started with the announcement of Plancks quantum theory in 1901 and culminated in the dropping of atom bombs in Hiroshima and Nagasaki in 1945 .

The experiments and theoretical models led to the following conclusions, which were completely contrary to the classical concepts that existed in the pre 1900 period .The intensity of electromagnetic radiation is not continuously distributed. For a given frequency of radiation the unit of energy E is proportional to the frequency, .

The total energy of electromagnetic radiation of a given intensity is expressed as integral multiples of this unit . If each unit has an assigned intensity, then intensity and the energy of electromagnetic radiation are quantized.In other words the radiation behaves like a particle whose energy is hv. The total intensity is the sum of the intensities of total number of particles called Photons. BASIS; Planck's interpretation of blackbody radiation, photoelectric effect, Compton effect. In terms of the traditional wave concept of electromagnetic radiation, each photon can be described as a wave packet .The second important conclusion was that classical mechanical Newtons laws of motion couldnt be applied to particles in the microscopic world. i.e., the world of protons, electrons, neutrons etc. These systems though posses finite mass also have the characteristics of waves. BASIS; Davison and Germer ; Electron diffraction experiment , Louis de Broglie hypothesis, Heisenberg's uncertainty principle. In general, matter has wave characteristics but the latter behavior is manifested to significant extent only in the microscopic world. It is not of consequence in the ordinary macroscopic world. The third important result is the conclusion that matter and energy are interconvertible . Einsteins famous relationship E (1) For electromagnetic radiation, m0=0 (rest mass) and hence E 2 = p For material particles, E2 = m02 c2 {v2 + c2} ~ m02 c4 v<<c
2 2

c2+m02 c4 c2

or E = m0c2 since

Now we will accept these conclusions and see how classical laws are inadequate to describe the behavior of atoms and molecules and subatomic particles . Experimental details BLACK BODY RADIATION: When a black body is heated, radiation is emitted and it is analyzed for the total energy and the frequency. The energy distribution is given by the following graph.

Classical theory based on the theory of equipartition predicts the same energy for different frequencies, which is in contradiction to experience. Two assumptions have to be made to explain this curve. 1. Energy of an oscillator is proportional to frequency E v i.e., E = hv 2. Energy distribution occurs in the units of hv and hence it is quantized.These prepositions were strengthened and confirmed by Einstein who showed that only a quantum model for electromagnetic radiation would explain photoelectric effect. PHOTOELECTRIC EFFECT When light strikes a metal surface electrons are emitted with certain kinetic energies.

1 Irrespective of intensity, radiation below certain frequency does not eject the electrons. 2. The kinetic energies of the emitted electrons are independent of the intensity of radiation. Both these observations lead to the conclusion that the energy of the radiation depends only on the frequency and not on the intensity. 3. The number of electrons emitted is proportional to the intensity. Light radiation is quantized. i.e., One photon interacts with one electron and is captured by the electron. The electronic energy is increased by hv ; part of it is used to overcome the binding energy of the electron in the metal . the remaining part is manifested as the kinetic energy of the particle . This means hv binding energy Kinetic (2) energy = hv -U (binding energy)

This experiment establishes the fact that electromagnetic radiation is quantized. COMPTON EFFECT: This is an experiment done with high energy photons ( x - rays ). The photon energy is not transferred completely to the electron . X- rays with known frequency strike electron in matter and get scattered .The scattered radiation has longer . Here again the experiment can be interpreted as one to one interaction of a photon with electron . The photon strikes an electron , transfers part of its momentum and comes out with lesser energy. One can relate the frequency of radiation and the momentum of photon using Einsteins eqn . E 2 = m0 2 c4 + p2 c2 [ rest mass ] for photons m0 = 0

hence E = p c = hv = h c / or = h/p In 1924 de Broglie predicted that electrons and similar particles can be associated with a given by the same relation as above . ie ., = h / p = h/ mv Summarizing , 1. Light radiation , though is propagated as waves , also has corpuscular nature . 2. matter also has complimentary wave character. (3)

At the beginning of the twentieth century, experimentation revealed that electromagnetic radiation has particle-like properties and as a result, it was theorized that all particles must also have wavelike properties. The idea that particles have wavelike properties resulted from the observation that a monoenergetic beam of electrons could be diffracted in the same way a monochromatic beam of light can be diffracted. The diffraction of light is a result of its wave character;hence, there must be an abstract type of wave character associated with small particles. De Broglie summarized the universal duality of particles and waves in 1924 and proposed that all matter has an associated wave with a wavelength, that is inversely proportional to the momentum, p, of the particle (verified experimentally in 1927 by Davison and Germer).The constant of proportionality, h, is Plancks constant. p = h/ The de Broglie relation fuses the ideas of particle-like properties (i.e. momentum) with wave-like properties (i.e. wavelength). This duality of particle and wave properties will be the theme throughout the rest of the text. The de Broglie relationship not only provides for a mathematical relationship for the duality of particles and waves, but it also begins to hint at the idea of quantization in mechanics. If a particle is in an orbit, the only allowed radii and momenta are those where the waves associated with the particle will interfere non-destructively as they wrap around each orbit. Momenta and radii where the waves destructively interfere with one another are not allowed, as this would suggest an annihilation of the particle as it orbits through successive revolutions. For any theory to be valid it must predict classical mechanics at the limit of macroscopic particles (called the Correspondence Principle). In the de Broglie relationship, the wavelength is an indication of the degree of wave-like properties. Consider an automobile that has a mass of 1000. kg travelling at a speed of 50km per hour. The momentum of the automobile is

Dividing this result into Plancks constant yields the de Broglie wavelength.

Considering the dimensions of an automobile, this wavelength would be beyond the accuracy of the best measuring instruments. If an electron were travelling at a speed of 50.0 km/hr, the corresponding de Broglie wavelength would be about 5X10-5 m.. This wavelength is quite significant compared to the average radius of a hydrogen ground-state orbital (1s) of approximately

10-11m. The wave-like properties in our macroscopic world do not disappear, but rather they become insignificant. The wave-like properties of particles at the atomic scale (i.e. small mass) become quite significant and cannot be neglected. The magnitude of Planks constant ( 6.63X 10-34 Js), is so small that only for very small masses is the de Broglie wavelength significant.