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    Chemical Bonding

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    AYAN KUMAR
    1. The document introduces chemical bonding and quantum mechanics concepts such as molecular orbitals, linear combination of atomic orbitals, and the variation method. 2. It uses the hydrogen molecule (H2) as a simple example to illustrate how molecular orbitals are formed from the linear combination of atomic orbitals and how the energy of these molecular orbitals can be calculated. 3. The energy levels of the bonding and antibonding molecular orbitals are shown in an energy level diagram, with the bonding orbital lower in energy and thus stable.

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    Chemical Bonding

    Uploaded by

    AYAN KUMAR
    13 views72 pages
    1. The document introduces chemical bonding and quantum mechanics concepts such as molecular orbitals, linear combination of atomic orbitals, and the variation method. 2. It uses the hydrogen molecule (H2) as a simple example to illustrate how molecular orbitals are formed from the linear combination of atomic orbitals and how the energy of these molecular orbitals can be calculated. 3. The energy levels of the bonding and antibonding molecular orbitals are shown in an energy level diagram, with the bonding orbital lower in energy and thus stable.

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    Chemical Bonding, Inorganic Chemistry

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    1. The document introduces chemical bonding and quantum mechanics concepts such as molecular orbitals, linear combination of atomic orbitals, and the variation method. 2. It uses the hydrogen molecule (H2) as a simple example to illustrate how molecular orbitals are formed from the linear combination of atomic orbitals and how the energy of these molecular orbitals can be calculated. 3. The energy levels of the bonding and antibonding molecular orbitals are shown in an energy level diagram, with the bonding orbital lower in energy and thus stable.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
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    13 views72 pages

    Chemical Bonding

    Uploaded by

    AYAN KUMAR
    1. The document introduces chemical bonding and quantum mechanics concepts such as molecular orbitals, linear combination of atomic orbitals, and the variation method. 2. It uses the hydrogen molecule (H2) as a simple example to illustrate how molecular orbitals are formed from the linear combination of atomic orbitals and how the energy of these molecular orbitals can be calculated. 3. The energy levels of the bonding and antibonding molecular orbitals are shown in an energy level diagram, with the bonding orbital lower in energy and thus stable.

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    INTRODUCTION TO

    CHEMICAL BONDING
    Failure of Classical Mechanics
    • Total energy, E = ½ mv2 + V(x)
    • p = mv (p = momentum)
    • E = p2/2m + V(x) ………..Eq.1
    • Newton’s second law, which is a relation
    between the acceleration d2x/dt2 of a
    particle and the force F(x) it experiences.
    • Therefore, v = p/m
    • Or, p• = F(x),
    • Continuos variation of energy is possible.
    • Certain experiments done in late 19th
    century and early in this century gave
    results, totally at variance with the
    predictions of classical physics. All
    however, could be explained on the basis
    that, classical physics is wrong in allowing
    systems to possess arbitrary amounts of
    energy. For example, photoelectric effect.
    A young Max Planck was to give a lecture on radiant heat. When he
    arrived he inquired as to the room number for the Planck lecture. He
    was told, "You are much too young to be attending the lecture of the
    esteemed professor Planck."

    • Max Planck E = h
    Photoelectric Effect.
    Major objections to the
    Rutherford-Bohr model
    • We are able to define the
    position and velocity of each
    electron precisely.
    • In principle we can follow the
    motion of each individual
    electron precisely like planet.
    • Neither is valid.
    • It is impossible to specify the exact
    position and momentum of a particle
    simultaneously.
    • Uncertainty Principle.
    • x p  h/4 where h is Plank’s
    Constant, a fundamental constant with
    the value 6.62610-34 J s.
    Einstein could never accept some of the revolutionary
    ideas of quantum mechanics("God does not play
    dice"). When reminded in 1927 that he revolutionized
    science 20 years earlier, Einstein replied, "A good joke
    should not be repeated too often."
    Einstein

    KE 1/2mv2 = h- 
    •  is the work function
    • h is the energy of the incident light.
    • Light can be thought of as a bunch of
    particles which have energy E = h. The
    light particles are called photons.
    If light can behave as particles,why
    not particles behave as wave?
    Louis de Broglie

    • Particles can behave as wave.


    • Relation between wavelength  and the
    mass and velocity of the particles.
    • E = h and also E = mc2,
    • E is the energy
    • m is the mass of the particle
    • c is the velocity.
    • E = mc2 = h
    • mc2 = h
    • p = h / { since  = c/}
    •  = h/p = h/mv
    • This is known as wave particle duality
    Wave equation?
    Schrödinger Equation.
    • Energy Levels
    • Most significant feature of the Quantum
    Mechanics: Limits the energies to discrete
    values.
    • Quantization.
    Classical Equation: Electromagnetic Radiation:

    u = Amplitude

    Separate Variables
    Introduce standard wave equation solution for f(t)

    We can write

    Total Energy
    Solution

    From de Broglie Equation

    2/v2 in terms of 

     = 2 and  = v
    Therefore form

    Schroedinger Equation in One Dimension


    Schroedinger Equation in Three dimension

    H = E

    ·H = - ħ2/2m 2 + V; Hamiltonian operator


    How to write Hamiltonian for
    different systems?
    • Hydrogen atom:
    • KE = ½ m (vx2 + vy2 + vz2)
    • PE = -e2/r, (r = distance between the
    electron and the nucleus.)
    • H = {(-h2/82m) 2 –e2/r}
    • 2  + 82 m/h2 (E+e2/r)  = 0
    • If the effective nuclear charge is Ze
    • H = {(-h2/82m )2 –Ze2/r}
    H2+ molecule

    e (x,y,z)

    ra rb

    A(+e) RAB B(+e)


    • PE = V = -e2/ra – e2/rb + e2/Rab
    • H = -h2/82m 2( – e2/ra - e2/rb + e2/Rab)

    • The Wave equation is

    • 2  + 82 m/h2 (E+ e2/ra + e2/rb – e2/Rab) 


    =0
    • Characteristics of Wave Function
    Born has been described as
    a moody and impulsive person.
    He would tell his student,
    "You must not mind my being
    rude. I have a resistance
    against accepting something
    new. I get angry and swear
    but always accept after a
    time if it is right."
    Characteristics of Wave
    Function
    • Heisenberg’s Uncertainty principle: We
    can never know exactly where the
    particle is.
    • Let  (x, y, z) be the probability function,
    •  d = 1
    • Our knowledge of the position of a
    particle can never be absolute.
    Connection with Wave Function

    • Let  (x, y, z) be the solution of the wave


    equation for the wave function. Then we
    may anticipate that
    •  (x, y, z)  2 (x, y, z)
    • Choosing a constant in such a way that
    the  is converted to =
    •  (x, y, z) = 2 (x, y, z)
    • 2 d = 1
    • Normalized wave function.
    • If the function is not:
    • 1/N2 = 2(x, y, z) d

    • If  is complex then 2 is replaced by *.


    Unacceptable and Acceptable wave
    functions:
    • Acceptable:
    • .For electron bound to an atom/molecule,
    the wave function must be every where
    finite.
    • .Single valued.
    • .Continuous.
    • .Gradient (d/dt) must be finite
    • .∫2 d is finite, so that  can be
    normalized.
    • Stationary States
    • E = Eigen Value ; is Eigen Function
    One Dimensional Box
    • V= a V=

    • V V

    •x=0 x=a
    The Wave Eqn. is
    • d2/dx2 + 82m/h2[E] = 0
    • d2/dx2 + k2 = 0
    • k2 = 82m/h2[E]
    • Solution is
    •  = C cos kx + D sin kx
    • Applying Boundary conditions:
    •  = 0 at x = 0  C = 0
    •  = 0 at x = a
    •  = 0 at x = a
    • D sin ka = 0
    • sin ka = 0 or ka = n
    • n = 0, 1, 2, 3, 4…….
    • n = D sin (n/a)x
    • k2 = 82m/h2[E] or E = k2h2/ 82m
    • E = n2 h2/ 8ma2
    • n = 0 not acceptable: n = 0
    • Lowest kinetic Energy = E0 = h2/8ma2
    Need for Effective Approximate Method of
    Solving the Wave Equation.

    • Born Oppenheimer Principle.


    • How can we get the most suitable
    approximate wave function?
    • How can we use this approximate wave
    function to calculate energy E?
    Variation Method

    • H = E
    •  H =  E = E 
    • E = H  d/2 d
    • If  is complex, E =  *H  d/  * d
    • /H/  //  ……4
    • Bra-Ket notation
    • E can be calculated. If the wave function is
    not known, we can either make an educated
    guess or use Variation Theorem.
    • The nature of the equation 4 suggest that
    even if  is not correct, we should consider a
    quantity E with dimension of energy, which is
    related to  by

    • E = /H/  // 
    • 1  E1
    • 2 E2
    • The Variation Theorem tells that
    • E1 , E2 Eg, Eg ground state energy
    • E1  E2,
    • E2 and 2 is the better approximation.
    • We can chose a whole family of wave
    function at the same time, like trial function
    with one or more variable parameters C1, C2,
    C3,….
    • Then E is function of C1, C2, C3 …….etc. C1, C2,
    C3 …. Etc. are such that E is minimized with
    respect to them.
    • We will utilize this method in explaining
    chemical bonding.
    Chemical Bonding

    • Two existing theories,


    • Molecular Orbital Theory (MOT)
    • Valence Bond Theory (VBT).
    • Molecular Orbital Theory
    • MOT starts with the idea that the
    quantum mechanical principles applied
    to atoms may be applied equally well to
    the molecule
    We can write the following
    principles
    • Each electron in a molecule is described by a
    certain wave function  - Molecular Orbital
    (MO).
    • Each  is defined by certain quantum numbers,
    which govern its energy and its shape.
    • Each  is associated with a definite energy value.
    • Each electron has a spin, ± ½ and labeled by its
    spin quantum number ms.

    • When building the molecule- Aufbau Principle


    (Building Principle) - Pauli Exclusion Principle.
    Simplest possible molecule - H2 +

    two nuclei and a single electron.


    • Let the two nuclei be labeled as A and B.
     A  B.
    • Since the complete MO has
    characteristics separately possessed by
    A and B,
    •  = CA  A + CB B
    • or  = N(A + B)
    •  = CA/CB, and N - normalization
    This method is known as Linear
    Combination of Atomic Orbitals or
    LCAO.
    • A and B are same atomic orbitals
    except for their different origin.
    • By symmetry A and B must appear
    with equal weight and we can therefore
    write
    • 2 = 1, or  = ±1
    • Therefore, the two allowed MO’s are
    •  =  A±  B
    For A+ B we can now
    calculate the energy
    • From Variation Theorem we can write the
    energy function as

    • E = A+B/H/A+B/A+B/ A+B
    Let us take the nominator of the right
    hand side of the above equation:

    • A+B/H/A+B = A/H/ A +


    • B/H/ B +
    • A/H/ B +
    • B/H/ A
    • = A/H/ A + B/H/ B +2A/H/
     B
    • Now A/H/ A or B/H/ B is the
    ground state energy of a hydrogen atom
    Now A/H/ A or B/H/ B is the ground state energy of
    a hydrogen atom

    • let us call this as EA


    • A/H/ B = B/H/ A =  =
    resonance integral.
    The denominator:
    • A+B/ A+B = A/A +
    • B/B +
    • A/B +
    • B/A
    • = A/A + B/B + 2A/B
    • A/B = B/A = S, Overlap
    integral. Also we know that A and B
    are separately normalized, so A/A =
    B/B = 1
    • E =[2EA + 2] / 2(1 + S)
    • Or E+ = [EA + ]/ (1 + S)
    • Similarly, E- = [EA - ]/ (1 – S)
    • Numerically S is very small, so if we neglect
    S, we can write
    • E± = EA ± 
    Energy level diagram

    EA - 

    B --------------------------- B

    EA + 

    Figure 5
    Homonuclear Diatomics
    • MOs may be classified according to-
    (i)Their symmetry around the molecular
    axis
    • (ii)Their bonding and antibonding
    character.
    • (iii) The atomic orbitals into which they
    separate at large internuclear
    distances.
    • 1s1s*2s2s*2py(2p) =
    z(2p)y*(2p)z*(2p)2p*.
    In drawing this diagram we
    have ignored one fact.
    • We have assumed that there is no
    interaction between 2s and 2p orbitals.
    • This is not true.
    • Thus from Li to at least N there is strong
    interaction between the 2s and 2p
    orbitals.
    Heteronuclear Diatomics

    • In the case of heteronuclear diatomic molecules whatever


    arguments are presented above are valid.
    • The only difference is that the energy level diagram is not
    symmetrical.
    • The bonding MOs are closer to the atomic orbitals which
    are lower in energy
    • The antibonding MOs are closer to those higher in energy
    Molecular Orbital Theory of Solids

    • The MOT extended to account for the properties of solids.


    • Aggregations of virtually infinite number of atoms.
    • Metals: (i)High Electrical Conductivity
    • (ii) Thermal conductivity
    • (iii) Luster
    • (iv) Malleability.

    All these properties can be explained by the ability of the


    individual atom to contribute electrons to a common sea.
    All these properties are due to high mobility of electrons.
    Electronic conduction -

    • semiconductors.

    • Temperature dependence of the electrical conductivity.

    • Metals - the conductivity decreases with temperature

    • Semiconductors - increases.
    Electrons occupy the orbitals in the band in accord
    with the building-up principle.

    • If each atom supplies one s electron, then at T = 0 the lowest


    1/2N are occupied.

    • The highest occupied orbital at T = 0 is called the Fermi level

    • At temperature above absolute zero, the population P of the


    orbitals is given by Fermi-Dirac distribution
    P = 1/e(E-EF)/kT + 1
    EF is the Fermi energy, the energy of the level for which P = ½.
    The Fermi energy depends on the temperature and at T = 0 is
    equal to the energy of the Fermi level.

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