Quantum Mechanical

Models
Bohr’s model inadequacy
• Failed to explain structure and behavior of atoms containing more
than one electron
• Reason - Not considering the repulsions between multiple electrons around
nucleus
• Also electrons do not follow a clearly defined circular orbit at a fixed
distance from nucleus
• Rather electrons are localized within a region of space called orbitals
• Hence it is impossible to pinpoint exactly where an electron is at any given
time
Heisenberg’s uncertainty principle
• It is impossible to determine simultaneously with perfect accuracy
the momentum and position of an electron. This is known as
Heisenberg’s uncertainty principle.
• So to find position electron has to stop (removing momentum) and to
find momentum it has to be moving (changing position)
Explanation
• Every object in the universe has wave as well as particle nature
• Particle is defined as one that exists at a single place at any instant in
time
• Waves are disturbances that spread out in space as ripples on water
identified based on its wavelength (difficult to assign a position)
• Wavelength is related to momentum (m x v)
• High momentum corresponds to short wavelength
• Thus practically we don’t notice wavy nature of objects bcoz of their
large masses (but it is opposite for sub-atomic particles)
Cont
• To find both position and momentum principle of superimposition is
used

• By further addition of many waves we can

narrow the wavier region and a wave packet
with clear wavelength in one region
Position and Momentum uncertainty
Quantum Numbers
• As per modern atomic theory any electron in an atom can be completely described
by 4 quantum no.s
• n, l, ml, ms
• Pauli’s exclusion principle
• No two electrons in a given atom can possess same set of 4 quantum nos
• Position and energy of an electron described by its quantum nos are known as its
energy state
• The value of n limits the values of l, which in turn limit the values of m l
• i.e. for a given value of n, only particular values of l are permissible, given a value of l, only
particular values of ml are permissible
• quantum nos qualitatively give info about the size, shape, and orientation of the
orbitals
Principal Quantum number (n)
• This is the one used in Bohr’s model
• Can theoretically take value of any +ve integer
• Max no of electrons a shell can hold = 2n2
• We already discussed some concepts regarding n
• Energy level and radius are directly proportional to n
• Difference in energy b/w 2 shells decreases as distance from nucleus
increases
Azimuthal Quantum number
• Designated by l
• Refers to shape and no of subshells of a shell
• Significance
• Important implications for chemical bonding & bond angles
• For a given n
• Range of possible values of l are o to n-1
• Example
• Within 1st shell i.e. n=1, possible value for l = 0 & 0, 1 for n=2
Representation
• While the pqn is represented by number, aqn is designated by letter
• l=0 subshell  s
• l=1 subshell  p
• l=2 subshell  d
• l=3 subshell  f
• Example
• Electron in shell n=4 and subshell l=2 is said to be 4d subshell
• Max no of electrons within a subshell = 4l+2
Energy variation
• Directly proportional to l value
• Energies of subshells from different principal energy levels may overlap
• Example – 4s subshell has less energy than 3d
Magnetic quantum number
• Designated as ml
• Specifies the particular orbital within a subshell where an electron is
most likely to be found at a given moment in time
• Each orbital can hold a max of 2 electrons
• Possible values are integers b/w –l to +l including 0
• Example
• For s subshell, l=0 possible value is 0 only
• For p, l=1, -1, 0, 1 are the values
• For d -2 to 2 and f -3 to 3
Shapes of orbitals
• Depends on subshell they are found
• Orbitals in
• s subshell  spherical
• p subshell orbitals  dumbbell shaped along 3 axes (px, py, pz)
• Shapes of d & f are more complex
Points to keep in mind
• For any value of l
• There will be 2l+1 possible values for mqn (m)
• Hence for any n
• This produces n2 orbitals
• So max no of electrons will be 2n2
• Since 2 electrons per orbital
• From all these we can explain why periodic table has different no of
groups for different blocks
Electron Configuration
• Patterns by which subshells are filled
• Also designates no of electrons within each energy level and subshell
• Spectroscopic notation
• 1st number denotes principal energy level
• Letter designates subshell
• Superscript gives no of electrons in subshell
• Example – 3p5 indicates
• 5 electrons in p subshell of 3rd principal energy level
• This also implies all the lower energy levels are filled (1s, 2s, 2p, 3s)
Electron subshell Flow diagram
How to write electronic configuration
• Aufbau principle
• Electrons fill from lower energy level to higher energy subshells
• Aka building up principle
• Each subshell will fill completely before electrons enter into next one
Alternate way for electronic configuration
• Lowest subshells are as follows
• For s – 1s
• For p – 2p
• For d – 3d
• For f – 4f
• So just by reading through periodic table we can fill the subshells
• For the larger atomic numbers, writing electronic configurations
become large
• So the nearest previous inert gas is helpful to make it short
Example – Osmium (Z=76)
• Nearest Noble gas preceding is of Xenon (Z=54)
• Hence EC is written starting with [Xe]
• See the periodic table to complete the rest
• After Xe we pass through 6s, then 4f and then 5d
• Osmium is the 6th element in 5d subshell
• Therefore the final EC is [Xe] 6s24f145d6
Electronic Configuration for ions
• Similar to neutral atoms
• But after writing EC for neutral atom
• Add the electrons if it is anion
• Subtract if cation
• While removing if 2 subshells have same energy choose the one with
high ‘l’ value
• Example
• fluorine’s electron configuration is [He] 2s22p5
• then F– is [He] 2s22p6
• Do it for Fe+3
Hund’s Rule
• In subshells with more than one orbital, electrons fill according to
Hund’s rule
• It states that within a given subshell, orbitals are filled such that there
are a maximum number of half-filled orbitals with parallel spins
• Just like a bus seat
• Reason
• Electrons try to avoid repulsion
Example
• Nitrogen
• 2 ‘s’ orbitals fill completely
• But 3 p orbitals will each contain one electron with parallel spins

• Iron - 26
Significance of Hund’s rule
• We can say that half-filled and fully filled orbitals have lower energies (higher stability) than
other states.
• Special ECs
• chromium & copper
• Chromium (Z = 24) should have [Ar] 4s23d4
• However, moving one electron from the 4s subshell to the 3d subshell allows the 3d subshell to be half-
filled: [Ar] 4s13d5
• So though energetically unfavorable, offer of extra stability by half-filled 3d subshell
outweighs it
• Similarly Copper (Z=29) should have [Ar] 4s23d9
• But it prefers [Ar] 4s13d10
• This holds good for ‘f’ orbital too. However the same doesn’t hold for s & p orbital as it
doesn’t outweigh the effort
Magnetic properties
• Presence of paired or unpaired electrons affects the chemical and
magnetic properties of an atom or molecule
• Materials composed of atoms with unpaired electrons will orient their
spins in alignment with a magnetic field, and the material will thus be
weakly attracted to the magnetic field. These are called Paramagnetic
materials
• Paramagnetism
• When a magnetic field causes parallel spins in unpaired electrons and there
by cause attraction
Diamagnetism
• Materials consisting of atoms that have
only paired electrons will be slightly
repelled by a magnetic field and are said
to be diamagnetic
• Given sufficiently strong magnetic fields
beneath an object, any diamagnetic
substance can be made to levitate
• Applications
• MAGLEV
Octet rule
• The octet rule is a chemical rule of thumb that reflects the
observation that elements tend to bond in such a way that each atom
has eight electrons in its valence shell, giving it the same electronic
configuration as a noble gas
Valence electrons
• Electrons in outermost energy shell
• Can be easily removed and available for bonding
• i.e. active electrons of an atom (determine chemical behavior)
• Example - Groups 1 and 2 – only highest s subshell electrons are
valence electrons
• Special Property
• Elements in period 3 from Na and below may accept electrons into their ‘d’
subshell allowing them to hold more than 8 electrons in their valence shell
• This is a violation of octet rule
Assignment
• Which electrons are the valence electrons of vanadium, selenium,
and the sulfur atom in a sulfate ion?
• If given the following quantum numbers, which element(s) do they
likely refer to? (Assume that these quantum numbers describe the
valence electrons in the element.)
• orbital diagram for a neutral oxygen (O) atom and an O2– ion
• Magnetic resonance angiography (MRA) is a technique that can resolve
defects like stenotic (narrowed) arteries. A contrast agent like gadolinium
or manganese injected into the blood stream interacts with the strong
magnetic fields of the MRI device to produce such images. Based on
their orbital configurations, are these contrast agents paramagnetic or
diamagnetic?
•Q