Basic concepts in PHYSICAL CHEMISTRY

Classical mechanics & Quantum mechanical It looks at molecules as a collection of atoms and bonds

. Classical mechanics does not correctly describe the behavior of very small particles, such as electrons and nuclei of atoms; the behavior of such microscopic particles is describes by quantum mechanics, the key features of this mechanics is the quantization of energy.

In 1926 Erwin Schrdinger proposed equation which, when solved, gives energy and many properties of a stationary state of molecule. It is position as control to quantum mechanics. For particular of mass (m) moving in one dimension with energy E the equation is: (-/2m) (d2/dx2)+V =E .(1) Where V, which may be depended on the position, is the potential energy of the particle, (which is convenient modification of Planks constant =h/2).

 the motion of atoms and subatomic particles could be expressed using classical mechanics the laws of motion introduced in the seventeenth century by Isaac Newton, these laws were very successful at explaining the motion of everyday objects and planets.

 However, towards the end of the nineteenth century, experimental evidence accumulated showing that classical mechanics failed when it was applied to particles as small as electrons, which was solved by quantum mechanics.

 In classical physics, light is described as electromagnetic radiation, which is understood in terms of the electromagnetic field, an oscillating electric and magnetic disturbance that spreads as a harmonic wave through empty space, (vacuum). Such waves are generated by the acceleration of electric charge, as in the oscillating motion of electrons

 The wave travels at a constant speed called the speed of light, c, which is about 3 X 108 m S-I. As its name suggests, an electromagnetic field has two components, an electric field that acts on charged particles (whether stationary or moving) and a magnetic field that acts only on moving charged particles. The electromagnetic field is characterized by a wavelength, (lambda), the distance between the neighbouring peaks of the wave,

and its frequency, V , the number of cycles per second at which its displacement at a fixed point returns to its original value (Fig. 8.1). The frequency is measured in hertz, where 1Hz= 1 S-I. The wavelength and frequency of an electromagnetic wave are related by V=C

 Fig.8.1 The wavelength, of a wave is the peak-to-peak distance.

 Therefore, the shorter the wavelength, the higher the frequency. The characteristics of the wave are also reported by giving the wavenumber, , of the radiation, where

Wavenumbers are normally reported in (cm-1).

 Figure 8.2 summarizes the electromagnetic spectrum, the description and classification of the electromagnetic field according to its frequency and wavelength. White light is a mixture of electromagnetic radiation with wavelengths ranging from about 380 nm to about 700 nm (1 nm = 10-9 m).

 Our eyes perceive different wavelengths of radiation in this range as different colours, so it can be said that white light is a mixture of light of all different colours.

Wave-particle duality The energies of the electromagnetic field and of oscillating atoms are quantized. The observation that electromagnetic radiation of frequency v can possess only the energies 0, hv, 2hv, ... suggests that it can be thought of as consisting of 0, 1, 2, ... particles, each particle having an energy hv.

These particles of electromagnetic radiation are now called photons. The observation of discrete spectra from atoms and molecules can be pictured as the atom or molecule generating a photon of energy hv when it discards an energy of magnitude E, with E = hv.

Example 8.1 Calculate the number of photons emitted by a 100 W yellow lamp in 1.0 s. Take the wavelength of yellow light as 560 nm and assume 100 per cent efficiency. Method: Each photon has an energy hv, so the total number of photons needed to produce an energy E is E/hv. To use this equation, (E=Pt). Answer The number of photons is

Atomic and molecular orbital

Electronic configuration The building-up principle(Aufbau principle) The order of occupation of orbitals is Is 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s and each orbital may accommodate up to two electrons. As an example, consider the carbon atom, for which Z = 6, hence the ground-state configuration of C is Is2 2s2 2p2, or [He]2s22p2 However, we can be more precise: we can expect the last two electrons to occupy different 2p orbitals; [He]2s22px1 2p1y

Another rule of the building-up principle is: Electrons occupy different orbitals of a given subshell before doubly occupying any one of them. For instance, nitrogen (Z= 7) has the configuration [He] 2S22px 12py 12pz1, and only when we get to oxygen (Z = 8) is a 2p orbital doubly occupied, giving [He] 2S22px2 2py 12pz1 When electrons occupy orbitals singly we invoke Hund's maximum multiplicity rule: An atom in its ground state adopts a configuration with the greatest number of unpaired electrons.

The Pauli principle Lithium, with Z = 3, has three electrons. The first two occupy a Is orbital drawn even more closely than in He around the more highly charged nucleus. The third electron, however, does not join the first two in the Is orbital because that configuration is forbidden by the Pauli exclusion principle: No more than two electrons may occupy any given orbital, and if two do occupy one orbital, then their spins must be paired.

Electrons with paired spins, denoted , have zero net spin angular momentum, ms, because the spin of one electron is cancelled by the spin of the other. Specifically, one electron has ms = + the other has ms = - and they are orientated on their respective cones so that the resultant spin is zero (Fig. 10.18). The exclusion principle is the key to the structure of complex atoms, to chemical periodicity, and to molecular structure.

The multiplicity The multiplicity of a term is the value of 2S + 1. like 1S2 the electrons are all paired and there is no net spin: this arrangement gives a singlet term, IS. A single electron has S = , so a configuration such as [Ne] 3S1 can give rise to a doublet term, 2S. Likewise, the configuration [Ne]3pl is a doublet, 2p. When there are two unpaired electrons S = 1, so 2S +1= 3, giving a triplet term,

Atomic orbitals All s orbitals are spherically symmetric about the center of the atom whereas the shapes of p and d orbitals vary with angular direction. The three p orbitals have lobes pointing along the x, y, and z axes, respectively. The five d orbitals have more complex angular shapes.

Orbital approximation In principle, wavefunctions for a many-electron atom (more than two) describe the behavior of all the electrons simultaneously. However, the Schrdinger equation for such atoms cannot be solved exactly because each electron interacts with every other electron as well as with the nucleus. In the orbital approximation, the many-electron wavefunction is described as the product of the wavefunctions of the individual atomic orbitals occupied by each electron in the atom, =(1)(2) Each individual orbital can be considered like a hydrogenic atomic orbital.

Atomic and molecular spectra The most evidence for the quantization of energy comes from spectroscopy, the detection and analysis of the electromagnetic radiation absorbed, emitted, or scattered by a substance. The record of the intensity of light transmitted or scattered by a molecule as a function of frequency (v), wavelength (), or wavenumber ( = v/c) is called its spectrum. A typical atomic spectrum is shown in Fig. 8.10, and a typical molecular spectrum is shown in Fig. 8.11.

The obvious feature of both is that radiation is emitted or absorbed at a series of discrete frequencies. energy can be discarded or absorbed only in discrete amounts (Fig. 8.12). Then, if the energy of an atom decreases by E, the energy is carried away as radiation of frequency v, and an emission 'line', a sharply defined peak, appears in the spectrum. E= hv (8.10)

Types of Spectroscopy Emission spectroscopy is the analysis of the energy of photons emitted when a molecule moves from a higher to a lower energy state. Absorption spectroscopy is the analysis of the energy of photons absorbed from incident light by a molecule undergoing transition from a lower to a higher energy state. Scattering spectroscopy is the analysis of the energy lost or gained by a photon of incident light after it has undergone an energy exchange interaction with a molecule.

All spectroscopic measurements require a radiation source (for emission spectroscopy the excited sample acts as its own source), a dispersing element (to separate radiation into its component frequencies), and a detector (to measure radiation intensity). The exact nature of these components depends on the region of the electromagnetic spectrum under study. The intensity of a spectral transition is proportional to the concentration of molecules in the initial state of the transition, and (for absorption measurements) the path length of the radiation through the sample.

The Beer-Lambert law The Beer-Lambert law, log (I/I0)= [X]l, describes the exponential decrease in the transmittance, I/I0, of light through an absorbing sample, where I is the intensity of transmitted light, I0 is the intensity of incident light, l is the path length, [X] is the sample concentration, and is the absorption coefficient. The quantity log (I/I0) is called the absorbance (A). A = [X]l

Chemical Bonding Bonds are generated from combinations of the atomic orbitals from each of the bonding atoms, and the bond is mathematically described as a function of these atomic orbitals. Where the resulting bond has cylindrical symmetry about the bond axis, it is termed a (sigma) bond. Elements with accessible p orbitals may generate bonds by sidelong overlap of the orbitals to give a (pi) bond.

The valency of many elements is greater than that predicted from the number of unpaired atomic electrons. Promotionraising one electron from a pair into a higher energy orbitalcreates two additional unpaired electrons in an atom, and so increases the valency by two. The energy required for electron promotion is offset by the energy recouped in forming two additional chemical bonds.

Hybridization The shapes of polyatomic molecules are poorly described by pure atomic orbitals. Deviation of actual bond angles from the angles between pure atomic orbitals is accounted for by hybridization. Atomic orbitals are combined into hybrid orbitals, whose shape is defined by the geometry and proportion of the atomic orbitals. Sp3 hybrid orbitals are tetrahedrally arranged, sp2 hybrid orbitals are arranged in a trigonal planar fashion, and sp orbitals are linearly arranged. More complex geometric configurations may be obtained by hybridization involving d and f orbitals.

Molecular orbital energy levels may be represented by a molecular orbital energy level diagram, which illustrates the relative energy of the molecular and atomic orbitals, and their relationship. The bonding molecular orbital is of lower energy than that of the separate atomic orbitals, and the converse is true for the antibonding orbital. The available electrons are placed in pairs into the molecular orbitals, with the lowest energy molecular orbitals being filled first. In the hydrogen molecule, both electrons occupy the bonding molecular orbital, giving an overall bonding interaction. In He2, two electrons occupy each of the and * orbitals, giving no net bonding.

ELECTRONIC SPECTROSCOPY The separation of energy levels arising from different configurations of electrons in atomic and molecular orbitals usually corresponds to radiation in the visible and ultraviolet regions of the electromagnetic spectrum (wavelengths between700 and ~100 nm). Nuclei are sufficiently more massive than electrons that an electronic transition occurs so fast that the nuclei do not alter their relative positions during the transition.

The excitation of an electron from the bonding orbital of a C=C bond to the * antibonding orbital is called a * transition. The excitation of one of the lone pair electrons of the O atom in a C=O bond to the * antibonding orbital is called an n* transition. The energy of * and n* transitions shifts to longer wavelength radiation as conjugation of the C=C and C=O bonds increases. A charge transfer transition involves electron movement between the d orbital of a metal atom and a ligand.

Fluorescence and Phosphorescence Fluorescence is the emission of radiation directly following absorption of excitation radiation. It is usually shifted to frequencies lower than the absorption because some vibrational excitation is lost in molecular collisions. Phosphorescence is the slow emission of radiation after absorption ceases and usually emanates from a triplet state accessed by spin-forbidden intersystem crossing from the initial excited singlet state. Phosphorescence is slower than Fluorescence (10-12 10-6 s), with typical lifetimes of 10-6 10-1 s.

Nuclear chemistry Nuclear chemistry is the subfield of chemistry dealing with radioactivity, nuclear processes and nuclear properties. It is the chemistry of radioactive elements such as the actinides, radium and radon. It includes the study of the chemical effects resulting from the absorption of radiation within living animals, plants, and other materials. The radiation chemistry controls much of radiation biology, radiation has an effect on living things at the molecular scale, as the radiation alters the biochemicals within an organism,

the alteration of the biomolecules then changes the chemistry which occurs within the organism, this change then can lead to a biological mutation. In contrast, nuclear chemistry greatly assists the understanding of medical treatments (such as cancer radiotherapy) and has enabled these treatments to improve. It includes the study of the production and use of radioactive sources for a range of processes such as the use of radioactive tracers within industry, science and the environment; and the use of radiation to modify materials such as polymers.

Nuclear magnetic resonance (NMR) spectroscopy is commonly used in synthetic organic chemistry and physical chemistry and for structural analysis in macromolecular chemistry.

*A radioactive tracer, or radioactive label, is a chemical compound in which one or more atoms have been replaced by a radioisotope to explore the mechanism of chemical reactions by tracing the path that the radioisotope follows from reactants to products. Radioisotopesof hydrogen, carbon, phosphorus, sulphur, and iodine have been used extensively to trace the path of biochemical reactions. The power of the technique is due to the fact that radioactive decay is much more energetic than chemical reactions. Therefore, the radioactive isotope can be present in low concentration and its presence detected by sensitive radiation detectors.

Radioactivity Nuclei which contain the same number of protons but different numbers of neutrons are called isotopes of that element. The isotopes are written as Isotopes undergo identical chemical reaction since the number of protons and electrons which define the bonding characteristics are the same for each isotope. Most elements, like oxygen, have isotopes that are stable under normal conditions. Such stable isotopes do not emit ionizing radiation and do not spontaneously transform into atoms of a different element.

Isotopes that are unstable and decompose naturally into other elements, with the release of harmful subatomic particles and/or radiation, are known as radioisotopes. Radioactivity is the emission of subatomic particles and/or electromagnetic radiation accompanying these conversions (transmutations) from parent isotope to daughter isotope. The three common forms of radioactive emission are: -particles (helium-4 nuclei); -particles (electrons); and -rays (very short-wave electromagnetic radiation).

An -particle consists of two protons and two neutrons and is effectively the nucleus of a helium-4 atom, An example of -decay is the transmutation of the uranium-238 isotope to an isotope of thorium: A -particle is an electron. It therefore has a small mass, and a charge of 1 atomic charge unit. -decay occurs when a neutron spontaneously converts into a proton, which remains in the nucleus, and an electron, which is emitted.

Gamma () rays are very high energy photons often released during - and -decay processes when the daughter nuclide decays from an excited to a more stable state. Since -rays are photons of the electromagnetic spectrum they have no mass and no charge and travel at the speed of light. Photons of -rays are even more energetic than those of X-rays and are thus extremely penetrating and highly damaging. Thorium-234 isotope from the -decay of uranium-238 is accompanied by emission of -rays:

In all cases the mass or energy loss during radioactive decay can cause damage to the environment through the formation of reactive ions or free radicals. The extent of damage depends on the type of mass or energy emitted. The time taken for 50% of a radioactive sample to decay is called the half-life. Radioactivity is measured in units of bequerel and the absorbed dose in units of gray which is defined as one joule per kilogram.

Radiation chemistry Radiation chemistry is the study of the chemical effects of radiation on matter; this is very different to radiochemistry as no radioactivity needs to be present in the material which is being chemically changed by the radiation. An example is the conversion of water into hydrogen gas and hydrogen peroxide.

Uses within Biology Within living things, isotopic labels (both radioactive and nonradioactive) can be used to probe how the complex web of reactions which makes up the metabolism of an organism converts one substance to another. For instance a green plant uses light energy to convert water and carbon dioxide into glucose by photosynthesis. If the oxygen in the water is labeled, then the label appears in the oxygen gas formed by the plant and not in the glucose formed in the chloroplasts within the plant cells.

For biochemical and physiological experiments and medical methods, a number of specific isotopes have important applications. Stable isotopes have the advantage of not delivering a radiation dose to the system being studied. H-2 (deuterium), the stable isotope of hydrogen, is a stable tracer, the concentration of which can be measured by mass spectrometry or NMR. It is incorporated into all cellular structures.

N-15, the stable isotope of nitrogen, has also been used. It is incorporated mainly into proteins. Radioactive isotopes have the advantages of being detectable in very low quantities, in being easily measured by radiochemical methods, and in being localizable to particular regions of a cell. Many compounds with the radioactive atoms in specific positions can be prepared, and are widely available commercially.

In high quantities they require precautions to guard the workers from the effects of radiationand they can easily contaminate laboratory glassware and other equipment. For some isotopes the half-life is so short that preparation and measurement is difficult. For short-lived isotopes such as 11C, very rapid synthetic methods have been developed to permit the rapid addition of the radioactive isotope to the molecule.

Everyday Exposure to Radiation Nuclear radiation is all around us in the environment. Low-level radiation is found in the oceans and waterways, the rocks and soils, the plant materials and in the atmosphere surrounding the planet. Radioactive elements found in rock, soil, water, air, and in food. These naturally occurring radioisotopes such as carbon-14, potassium-40, thorium-223, uranium-238, polonium-218, and tritium(hydrogen-3) expose us to radiation.

Is This Exposure Dangerous? Any amount of radiation can be dangerous because of the potential effect that it has on living cells. Radiation can disrupt normal chemical processes of the cells, causing them to grow abnormally or to die. Cells that are altered by the radiation may go on to produce more abnormal cells - a process that could eventually lead to cancer. At low doses, cells are able to repair any damage rapidly. If one receives a very high dose, the cells may not be able to be replaced fast enough and tissues may fail to function properly. Guidelines for levels of exposure have been set by the Deparment of Energy as means of protecting the public.

Thermodynamics
Thermodynamics is the mathematical study of heat and its relationship with mechanical energy and other forms of work. In chemical systems, it allows determination of the feasibility, direction, and equilibrium position of reactions.

The first law Energy may be neither created nor destroyed, although the energy within a system may change its form. It is a result of the first law that energy in an open system may be exchanged with the surroundings as either work or heat but may not be lost or gained in any other manner. The energy of an isolated system is constant.

Internal Eneregy The sum of all the kinetic and potential energy in a system is the internal energy, U. Because it includes nuclear binding energy, and mass-energy equivalence terms, as well as molecular energies, it is not practical to measure an absolute value of U. Changes in the value of U and its relationship to other thermodynamic quantities are therefore used.

Work Work is energy in the form of orderly motion. The most common forms of work are pressurevolume work and electrical work. The work done by a system against a constant external pressure is given by w = pexV.

Enthalpy The enthalpy change, H, of a system is equal to its heat output at constant pressure. The standard state for a material is defined as being the pure substance at 1 atmosphere pressure, and at a specified temperature. If the value of H is negative the reaction is exothermic and if it has a positive value it is endothermic.

Entropy is a measure of the disorder ( Randomness) of a system. Work must be done to keep the entropy of the system low. Simply, all spontaneous changes in an isolated chemical system occur with an increase in entropy. Entropy, like temperature, pressure, and enthalpy, is also a state property and is represented by the symbol "S". Like enthalpy, you can calculate the change of S (S). S = Sfinal - S initial

The second law of thermodynamics; states that the entropy of an isolated system increases for irreversible processes and remains constant in the course of reversible processes. All systems tend to reach a state of equilibrium. The third law of thermodynamics The third law of thermodynamics states that the entropy of a perfectly crystalline solid at the absolute zero of temperature is zero.

Spontaneous and non-spontaneous processes A spontaneous process has a natural tendency to occur without the need for input of work into the system. Examples are the expansion of a gas into a vacuum, or flow of heat from a hot body to a cold one. A non-spontaneous process does not have a natural tendency to occur. Examples include the compression of a gas into a smaller volume.

Free energy The Gibbs free energy, G, is defined as G = HTS and at constant pressure and temperature, finite changes in G may be expressed as G=HTS. For a spontaneous process G<0 (constant pressure). Because most chemical and biochemical systems operate at constant pressure, the Gibbs free energy is more commonly encountered. The free energy change represents the maximum amount of work, other than volume expansion work, which may be obtained from a process.

Energy conversion in biological cells The whole of life's activities depends on the coupling of exergonic and endergonic reactions,for the oxidation of food drives other reactions forward. In biological cells, the energy released by the oxidation of foods is stored in adenosine triphosphate (ATP). The essence of the action of ATP is its ability to lose its terminal phosphate group by hydrolysis and to form adenosine diphosphate (ADP): ATP(aq) + H2O(l) ADP(aq) + Pi(aq) + Hp+(aq)

The biological standard values for ATP hydrolysis at 37C (310 K, blood temperature) are ~G= -31 Kj/mol, ~ H = -20 k] mol ", and ~ S = +34 J K-1 mol. The hydrolysis is therefore exergonic (G < 0) under these conditions and 31 Kj/mol is available for driving other reactions. Moreover, because the reaction entropy is large, the reaction Gibbs energy is sensitive to temperature. In view of its exergonicity the ADP-phosphate bond has been called a 'high -energy phosphate bond.

FUNDAMENTALS OF EQUILIBRIA An equilibrium is established when the rate of the forward and backward reactions are equal. This is denoted for a general reaction by:

At equilibrium, the Gibbs free energy changes for both the forward and backward reactions are zero. The equilibrium constant, K, is given by:

Where a is the activity of species.

For systems with negligible interaction between the reacting species (gases, neutral molecules and ions at low dilution) the equilibrium constant is given by:

where ci is the concentration of species i and c the standard concentration, is 1 mol dm3. The equilibrium constant can therefore be calculated from the concentrations of the reacting species in mol dm3.

An equilibrium can also exist between the same species in two different forms e.g. solid and liquid, liquid and gas. An equilibrium constant may also be produced for each of these systems. The standard Gibbs free energy for the forward reaction is related to the equilibrium constant by the expression:

The equilibrium position changes to oppose any perturbation to the system, in accordance with Le Chateliers principle. Thus increasing the pressure causes the equilibrium to shift to reduce the overall pressure rise. Increasing the temperature causes the equilibrium position to move in order to reduce the temperature rise. Adding a reactant or a product causes a change in equilibrium position that removes this species.

Collision theory Collision theory is a theoretical framework to explain the origin of the Arrhenius equation. The fundamental assumption of collision theory is that reaction occurs when two molecules collide with one another in a bimolecular reaction. As in the kinetic theory of gases collision theory makes the assumption that molecules are hard, structureless spheres which do not interact until they come into direct contact. It is further assumed that reaction only occurs when molecules collide with a kinetic energy greater than the activation energy.

The basis for this assumption is the reaction profile (Fig. 1) which plots the change in energy of the molecules as the reaction proceeds from reactants to products. The energy rises as the separation of the molecules becomes small enough for them to be in contact because bonds distort and break. To the right of the maximum in the profile the energy decreases as new bonds form and the product molecules separate to distances where there is no longer any interaction. The height of the energy barrier from reactants to products is identifiable with the activation energy, Ea, of the reaction. Molecules that collide with kinetic energy less than Ea bounce apart without reaction.

Molecular Symmetry Symmetry helps us understand molecular structure, some chemical properties, and characteristics of physical properties (spectroscopy), used with group theory to predict vibrational spectra for the identification of molecular shape, and as a tool for understanding electronic structure and bonding.

Group Theory: mathematical treatment of symmetry symmetry operation an operation performed on an object which leaves it in a configuration that is indistinguishable from the original configuration. symmetry elements the points, lines, or planes to which a symmetry operation is carried out.

Proper axes of rotation (Cn) Rotation with respect to a line (axis of rotation). Cn is a rotation of (360/n). C2 = 180 rotation, C3 = 120 rotation, C4 = 90 rotation, C5 = 72 rotation, C6 = 60 rotation Each rotation brings you to an indistinguishable state from the original.

Thus a C2 (180 rotation) about the z axis in H2O leaves the molecule unchanged:

A 180rotation about the y axis is not a symmetry operation

Planes and Reflection () If reflection of all parts of a molecule through a plane produced an indistinguishable configuration, the symmetry element is called a mirror plane or plane of symmetry. h(horizontal): plane perpendicular to principal axis v: Vertical, parallel to principal axis d: parallel to Cn and bisecting two C2 axes

Inversion, Center of Inversion (i) A center of symmetry: A point at the center of the molecule. (x,y,z) (-x,-y,-z). It is not necessary to have an atom in the center (e.g. benzene). Tetrahedral and triangles don't have a center of inversion symmetry.

Identity Simplest symmetry operation. All molecules have this element. If the molecule does have no other elements, it is asymmetric. The identity operation amounts to doing nothing to a molecule and so leaves any molecule completely unchanged.

Symmetry Point Groups Symmetry of a molecule located on symmetry axes, cut by planes of symmetry, or centered at an inversion center is known as point symmetry. Collections of symmetry operations constitute mathematical groups. Each symmetry point group has a particular designation.

Some Consequences of Molecular Symmetry As the point group of a molecule is identified, some statements about its properties can be done. Polarity A polar molecule is one having a permanent electric dipole moment. For instance these are NaCl, H2O, NH3, and many others. It is known that the rotational absorption transitions can occur only in polar molecules. The group theory give important instructions, how the molecular symmetry is related to the molecular polarity.

For instance, if a molecule belongs to the group Cn, where n > 1, then it cannot have a component of the dipole moment perpendicular to the symmetry axis, because a dipole moment which exist in one direction perpendicular to the axis is cancelled by an opposing dipole.

A dipole moment in these molecules can be only parallel to the molecular axis. The same is valid for any of the Cnv group molecule. The molecules which belongs to all other groups, but Cs, cannot have a permanent dipole moment, because they always have symmetry operations transforming one end of the molecule into another. Thus, only the molecules which belong to the Cn, Cnv, or Cs group can have a permanent dipole moment.

Chirality A chiral molecule is that cannot be transformed to itself with any mirror transformation. An achiral molecule can be transformed to itself with a mirror transformation. Chiral molecules are important because they are optically active in the sense that they can rotate the plane of polarized light passing through the molecular sample. Any molecule with a mirror plane is achiral.

SYMMETRY OF MOLECULAR VIBRATIONS Vibrational movement in polyatomic molecules is much more complicated than that of the diatomics. That is because much greater number of possible degrees of freedom of a polyatomic molecule. For instance, if there are N nuclei we need 3N coordinates to describe their motion.

However, if we want to study the vibrational motion of a molecule, we are not interested in the translational motion of the system as a whole, which can be described completely by three coordinates of the molecular center of mass, Xc, Yc,Zc.

Selection Rules: Infrared and Raman Spectroscopy Infrared energy is absorbed for certain changes in vibrational energy levels of a molecule. -for a vibration to be infrared active, there must be a change in the molecular dipole moment vector associated with the vibration. For a vibration mode to be Raman active, there must be a change in the net polarizability tensor -polarizability is the ease in which the electron cloud associated with the molecule is distorted The transition from the vibrational ground state to the first excited state is the fundamental transition

Raman spectroscopy; is a spectroscopic technique used to observe vibrational, rotational, and other lowfrequency modes in a system. It relies on inelastic scattering, or Raman scattering, of monochromatic light, usually from a laser in the visible, near infrared, or near ultraviolet range. The laser light interacts with molecular vibrations, phonons or other excitations in the system, resulting in the energy of the laser photons being shifted up or down. The shift in energy gives information about the vibrational modes in the system. Infrared spectroscopy yields similar, but complementary, information.