Introduction To Quantum Mechanics

Lecture 1
Introduction to Quantum Mechanics
Important Notes:
• Reference books:
– Quantum Chemistry, D. A. McQuarrie
– Quantum Chemistry, I. N. Levine
– Molecular Quantum Mechanics, by P. Atkins and R. Friedman
• Memorize the equations/constants/definitions that are marked in red only
• Solve numerical and analytical problems from the reference books
1
Physical Chemistry 1 CHM 321A/421 A
1.1 Quantization of Energy
Energy of a classical particle can vary continuously. But, quantization of energy was
required to explain several experiments.
• Max Plank assumed that blackbody radiation was caused by the oscillations of
electrons (1900). He could then explain the blackbody radiation by considering
that the energy of the oscillator is quantized as E = nhν, where n is an integer, h
is the Plank’s constant, with
h = 6.626 × 10−34 J s (1.1)
and ν is the frequency of the electromagnetic wave.
• Einstein could explain the photoelectric effect considering that light is composed
of particle-like entities (called photons), with each photon having an energy E =
hν (1905).
• Bohr’s model (1913) could explain H-atom emission spectrum by considering that
energies that an electron can posses in the hydrogen atom are given by
1
En = −constant × , n = 1, 2, · · ·
n2
1.2 Thought Experiment to Realise the Quantum Effect!

(Richard Feynman)
Let us first do a thought experiment, where a footballer randomly kicks several footballs
against a wall with two holes through which the ball can pass through, and another wall
with a detector that could measure the probability of seeing the football at a position
x; see Figure 1.1. The total probability P12 ( x ) is total probability of finding the football
at a point x on the wall can be clearly seen as the sum of probabilities of finding the
football when one of the holes is closed: i.e. P12 ( x ) = P1 ( x ) + P2 ( x ). We can attribute
this to “no interference” occurring in this experiment.
Now let us consider an experiment with water waves, where a wave source is con-
nected in water, and waves are created on the surface, and the experimental setup is
Page 2
Detector P1 <latexit sha1_base64="oqpQsBXPsMSxsgaRRnXvTZpABDc=">AAAB6XicbVBNS8NAEJ3Ur1q/qh69LBbBU0lEUG9FLx4rGltoQ9lsN+3SzSbsToQS+hO8eFDx6j/y5r9x2+agrQ8GHu/NMDMvTKUw6LrfTmlldW19o7xZ2dre2d2r7h88miTTjPsskYluh9RwKRT3UaDk7VRzGoeSt8LRzdRvPXFtRKIecJzyIKYDJSLBKFrpvtnzetWaW3dnIMvEK0gNCjR71a9uP2FZzBUySY3peG6KQU41Cib5pNLNDE8pG9EB71iqaMxNkM9OnZATq/RJlGhbCslM/T2R09iYcRzazpji0Cx6U/E/r5NhdBnkQqUZcsXmi6JMEkzI9G/SF5ozlGNLKNPC3krYkGrK0KZTsSF4iy8vE/+sflV3785rjesijTIcwTGcggcX0IBbaIIPDAbwDK/w5kjnxXl3PuatJaeYOYQ/cD5/ADxbjUs=</latexit>
x
<latexit sha1_base64="wrYRrS9nqr2/jTKdHNfdRLtLB0k=">AAAB53icbVBNS8NAEJ3Ur1q/qh69LBbBU0lFUG9FLx5bMLbQhrLZTtq1m03Y3Ygl9Bd48aDi1b/kzX/jts1BWx8MPN6bYWZekAiujet+O4WV1bX1jeJmaWt7Z3evvH9wr+NUMfRYLGLVDqhGwSV6hhuB7UQhjQKBrWB0M/Vbj6g0j+WdGSfoR3QgecgZNVZqPvXKFbfqzkCWSS0nFcjR6JW/uv2YpRFKwwTVulNzE+NnVBnOBE5K3VRjQtmIDrBjqaQRaj+bHTohJ1bpkzBWtqQhM/X3REYjrcdRYDsjaoZ60ZuK/3md1ISXfsZlkhqUbL4oTAUxMZl+TfpcITNibAllittbCRtSRZmx2ZRsCLXFl5eJd1a9qrrN80r9Ok+jCEdwDKdQgwuowy00wAMGCM/wCm/Og/PivDsf89aCk88cwh84nz9UTYzP</latexit>
<latexit
P12
<latexit sha1_base64="Q/UeRA5BDaIxg/2VPsYYZQUP3Rw=">AAAB7HicbVBNS8NAEJ3Ur1q/qh69LBbBU0mKoN6KXjxWMG2hDWWz3bRrN7thdyOE0P/gxYOKV3+QN/+N2zYHbX0w8Hhvhpl5YcKZNq777ZTW1jc2t8rblZ3dvf2D6uFRW8tUEeoTyaXqhlhTzgT1DTOcdhNFcRxy2gkntzO/80SVZlI8mCyhQYxHgkWMYGOldmuQe43poFpz6+4caJV4BalBgdag+tUfSpLGVBjCsdY9z01MkGNlGOF0WumnmiaYTPCI9iwVOKY6yOfXTtGZVYYoksqWMGiu/p7Icax1Foe2M8ZmrJe9mfif10tNdBXkTCSpoYIsFkUpR0ai2etoyBQlhmeWYKKYvRWRMVaYGBtQxYbgLb+8SvxG/bru3l/UmjdFGmU4gVM4Bw8uoQl30AIfCDzCM7zCmyOdF+fd+Vi0lpxi5hj+wPn8AXHEjpM=</latexit>
P2 <latexit sha1_base64="ksq7vieGY47U/4BgFJpuzIZ65So=">AAAB6XicbVBNS8NAEJ34WetX1aOXxSJ4KkkR1FvRi8eKxhbaUDbbTbt0swm7E6GE/gQvHlS8+o+8+W/ctjlo64OBx3szzMwLUykMuu63s7K6tr6xWdoqb+/s7u1XDg4fTZJpxn2WyES3Q2q4FIr7KFDydqo5jUPJW+HoZuq3nrg2IlEPOE55ENOBEpFgFK103+zVe5WqW3NnIMvEK0gVCjR7la9uP2FZzBUySY3peG6KQU41Cib5pNzNDE8pG9EB71iqaMxNkM9OnZBTq/RJlGhbCslM/T2R09iYcRzazpji0Cx6U/E/r5NhdBnkQqUZcsXmi6JMEkzI9G/SF5ozlGNLKNPC3krYkGrK0KZTtiF4iy8vE79eu6q5d+fVxnWRRgmO4QTOwIMLaMAtNMEHBgN4hld4c6Tz4rw7H/PWFaeYOYI/cD5/AD3ejUw=</latexit>
P12 = P1 + P2
<latexit sha1_base64="EyJX58PqBn/x3G5Aektf63RR59Q=">AAAB9HicbVBNS8NAEJ3Ur1q/qh69LBZBEEpSBPUgFL14jGBsoY1hs920SzebsLtRSuj/8OJBxas/xpv/xm2bg7Y+GHi8N8PMvDDlTGnb/rZKS8srq2vl9crG5tb2TnV3714lmSTUIwlPZDvEinImqKeZ5rSdSorjkNNWOLye+K1HKhVLxJ0epdSPcV+wiBGsjfTgBrnTGF+6gXPiBo2gWrPr9hRokTgFqUEBN6h+dXsJyWIqNOFYqY5jp9rPsdSMcDqudDNFU0yGuE87hgocU+Xn06vH6MgoPRQl0pTQaKr+nshxrNQoDk1njPVAzXsT8T+vk+no3M+ZSDNNBZktijKOdIImEaAek5RoPjIEE8nMrYgMsMREm6AqJgRn/uVF4jXqF3X79rTWvCrSKMMBHMIxOHAGTbgBFzwgIOEZXuHNerJerHfrY9ZasoqZffgD6/MH9ZWRDA==</latexit>
Detector I1
<latexit sha1_base64="Jl3gY+KLnL+wK7jLVsx3i9LsPis=">AAAB6XicbVBNS8NAEJ3Ur1q/qh69LBbBU0lEUG9FL3qraGyhDWWznbRLN5uwuxFK6E/w4kHFq//Im//GbZuDVh8MPN6bYWZemAqujet+OaWl5ZXVtfJ6ZWNza3unurv3oJNMMfRZIhLVDqlGwSX6hhuB7VQhjUOBrXB0NfVbj6g0T+S9GacYxHQgecQZNVa6u+l5vWrNrbszkL/EK0gNCjR71c9uP2FZjNIwQbXueG5qgpwqw5nASaWbaUwpG9EBdiyVNEYd5LNTJ+TIKn0SJcqWNGSm/pzIaaz1OA5tZ0zNUC96U/E/r5OZ6DzIuUwzg5LNF0WZICYh079JnytkRowtoUxxeythQ6ooMzadig3BW3z5L/FP6hd19/a01rgs0ijDARzCMXhwBg24hib4wGAAT/ACr45wnp03533eWnKKmX34BefjGzG4jUQ=</latexit>
Wave
Source x
<latexit
I2 I12
<latexit sha1_base64="zKxg8/LK3ccV6o3dL7EIE8hpiio=">AAAB7HicbVBNTwIxEJ3FL8Qv1KOXRmLiiewSE/RG9KI3TFwggQ3pli5Uuu2m7ZqQDf/Biwc1Xv1B3vw3FtiDgi+Z5OW9mczMCxPOtHHdb6ewtr6xuVXcLu3s7u0flA+PWlqmilCfSC5VJ8Saciaob5jhtJMoiuOQ03Y4vpn57SeqNJPiwUwSGsR4KFjECDZWat31M6827ZcrbtWdA60SLycVyNHsl796A0nSmApDONa667mJCTKsDCOcTku9VNMEkzEe0q6lAsdUB9n82ik6s8oARVLZEgbN1d8TGY61nsSh7YyxGellbyb+53VTE10GGRNJaqggi0VRypGRaPY6GjBFieETSzBRzN6KyAgrTIwNqGRD8JZfXiV+rXpVde8vKo3rPI0inMApnIMHdWjALTTBBwKP8Ayv8OZI58V5dz4WrQUnnzmGP3A+fwBnDI6M</latexit>
<latexit sha1_base64="jxJG23Jrcr1PnBpPII5UxYEXYKI=">AAAB6XicbVBNS8NAEJ3Ur1q/qh69LBbBU0mLoN6KXvRW0dhCG8pmO2mXbjZhdyOU0J/gxYOKV/+RN/+N2zYHbX0w8Hhvhpl5QSK4Nq777RRWVtfWN4qbpa3tnd298v7Bo45TxdBjsYhVO6AaBZfoGW4EthOFNAoEtoLR9dRvPaHSPJYPZpygH9GB5CFn1Fjp/rZX75UrbtWdgSyTWk4qkKPZK391+zFLI5SGCap1p+Ymxs+oMpwJnJS6qcaEshEdYMdSSSPUfjY7dUJOrNInYaxsSUNm6u+JjEZaj6PAdkbUDPWiNxX/8zqpCS/8jMskNSjZfFGYCmJiMv2b9LlCZsTYEsoUt7cSNqSKMmPTKdkQaosvLxOvXr2sundnlcZVnkYRjuAYTqEG59CAG2iCBwwG8Ayv8OYI58V5dz7mrQUnnzmEP3A+fwAzO41F</latexit>
Figure 1.1: Top: interference experiment with football. Bottom: interference experiment with
water waves
in Figure 1.1 (bottom). The waves pass through the holes and the detector detects the
amplitude of the wave arriving at the detector and measures it as the square of the
height of the wave. This is proportional to the energy of the wave arriving at the detec-
tor. In this case, clearly, interference takes place as the waves of same phase interfere
constructively and those out-of-phase interfere destructively. Amplitude of water wave
at a time t originated from hole 1 can be written as c1 eiωt , and that from hole 2 can
be written as c2 eiωt . Intensity is proportional to |c1 |2 or |c2 |2 if any one of the holes is
closed. If both the holes are open, then the intensity is proportional to |c1 + c2 |2 . Noting
that,
|c1 + c2 |2 = |c1 |2 + |c2 |2 + 2|c1 ||c2 | cos θ
where θ is the phase difference between c1 and c2 . The last term of the previous expres-
sion is responsible for the interference observed.
Let us now repeat the experiment with electrons; see the top panel of Figure 1.2.
Here, the detector counts the number of electrons reaching it at any point x. We realise
that every single electron reaches the detector as a one "full" electron and not a fraction
of one–electron. This is similar to football reaching the detector. Then, we would
think that, interference should not occur in this experiment. However, the probability
Page 3
Detector
P1 P12 <latexit sha1_base64="Q/UeRA5BDaIxg/2VPsYYZQUP3Rw=">AAAB7HicbVBNS8NAEJ3Ur1q/qh69LBbBU0mKoN6KXjxWMG2hDWWz3bRrN7thdyOE0P/gxYOKV3+QN/+N2zYHbX0w8Hhvhpl5YcKZNq777ZTW1jc2t8rblZ3dvf2D6uFRW8tUEeoTyaXqhlhTzgT1DTOcdhNFcRxy2gkntzO/80SVZlI8mCyhQYxHgkWMYGOldmuQe43poFpz6+4caJV4BalBgdag+tUfSpLGVBjCsdY9z01MkGNlGOF0WumnmiaYTPCI9iwVOKY6yOfXTtGZVYYoksqWMGiu/p7Icax1Foe2M8ZmrJe9mfif10tNdBXkTCSpoYIsFkUpR0ai2etoyBQlhmeWYKKYvRWRMVaYGBtQxYbgLb+8SvxG/bru3l/UmjdFGmU4gVM4Bw8uoQl30AIfCDzCM7zCmyOdF+fd+Vi0lpxi5hj+wPn8AXHEjpM=</latexit>
<latexit sha1_base64="oqpQsBXPsMSxsgaRRnXvTZpABDc=">AAAB6XicbVBNS8NAEJ3Ur1q/qh69LBbBU0lEUG9FLx4rGltoQ9lsN+3SzSbsToQS+hO8eFDx6j/y5r9x2+agrQ8GHu/NMDMvTKUw6LrfTmlldW19o7xZ2dre2d2r7h88miTTjPsskYluh9RwKRT3UaDk7VRzGoeSt8LRzdRvPXFtRKIecJzyIKYDJSLBKFrpvtnzetWaW3dnIMvEK0gNCjR71a9uP2FZzBUySY3peG6KQU41Cib5pNLNDE8pG9EB71iqaMxNkM9OnZATq/RJlGhbCslM/T2R09iYcRzazpji0Cx6U/E/r5NhdBnkQqUZcsXmi6JMEkzI9G/SF5ozlGNLKNPC3krYkGrK0KZTsSF4iy8vE/+sflV3785rjesijTIcwTGcggcX0IBbaIIPDAbwDK/w5kjnxXl3PuatJaeYOYQ/cD5/ADxbjUs=</latexit>
1
e-
Source x
<latexit
P2 <latexit sha1_base64="ksq7vieGY47U/4BgFJpuzIZ65So=">AAAB6XicbVBNS8NAEJ34WetX1aOXxSJ4KkkR1FvRi8eKxhbaUDbbTbt0swm7E6GE/gQvHlS8+o+8+W/ctjlo64OBx3szzMwLUykMuu63s7K6tr6xWdoqb+/s7u1XDg4fTZJpxn2WyES3Q2q4FIr7KFDydqo5jUPJW+HoZuq3nrg2IlEPOE55ENOBEpFgFK103+zVe5WqW3NnIMvEK0gVCjR7la9uP2FZzBUySY3peG6KQU41Cib5pNzNDE8pG9EB71iqaMxNkM9OnZBTq/RJlGhbCslM/T2R09iYcRzazpji0Cx6U/E/r5NhdBnkQqUZcsXmi6JMEkzI9G/SF5ozlGNLKNPC3krYkGrK0KZTtiF4iy8vE79eu6q5d+fVxnWRRgmO4QTOwIMLaMAtNMEHBgN4hld4c6Tz4rw7H/PWFaeYOYI/cD5/AD3ejUw=</latexit>
Detector
Light P1
<latexit sha1_base64="oqpQsBXPsMSxsgaRRnXvTZpABDc=">AAAB6XicbVBNS8NAEJ3Ur1q/qh69LBbBU0lEUG9FLx4rGltoQ9lsN+3SzSbsToQS+hO8eFDx6j/y5r9x2+agrQ8GHu/NMDMvTKUw6LrfTmlldW19o7xZ2dre2d2r7h88miTTjPsskYluh9RwKRT3UaDk7VRzGoeSt8LRzdRvPXFtRKIecJzyIKYDJSLBKFrpvtnzetWaW3dnIMvEK0gNCjR71a9uP2FZzBUySY3peG6KQU41Cib5pNLNDE8pG9EB71iqaMxNkM9OnZATq/RJlGhbCslM/T2R09iYcRzazpji0Cx6U/E/r5NhdBnkQqUZcsXmi6JMEkzI9G/SF5ozlGNLKNPC3krYkGrK0KZTsSF4iy8vE/+sflV3785rjesijTIcwTGcggcX0IBbaIIPDAbwDK/w5kjnxXl3PuatJaeYOYQ/cD5/ADxbjUs=</latexit>
P12
<latexit sha1_base64="Q/UeRA5BDaIxg/2VPsYYZQUP3Rw=">AAAB7HicbVBNS8NAEJ3Ur1q/qh69LBbBU0mKoN6KXjxWMG2hDWWz3bRrN7thdyOE0P/gxYOKV3+QN/+N2zYHbX0w8Hhvhpl5YcKZNq777ZTW1jc2t8rblZ3dvf2D6uFRW8tUEeoTyaXqhlhTzgT1DTOcdhNFcRxy2gkntzO/80SVZlI8mCyhQYxHgkWMYGOldmuQe43poFpz6+4caJV4BalBgdag+tUfSpLGVBjCsdY9z01MkGNlGOF0WumnmiaYTPCI9iwVOKY6yOfXTtGZVYYoksqWMGiu/p7Icax1Foe2M8ZmrJe9mfif10tNdBXkTCSpoYIsFkUpR0ai2etoyBQlhmeWYKKYvRWRMVaYGBtQxYbgLb+8SvxG/bru3l/UmjdFGmU4gVM4Bw8uoQl30AIfCDzCM7zCmyOdF+fd+Vi0lpxi5hj+wPn8AXHEjpM=</latexit>
e-
Source A
x
<latexit
P2
<latexit sha1_base64="ksq7vieGY47U/4BgFJpuzIZ65So=">AAAB6XicbVBNS8NAEJ34WetX1aOXxSJ4KkkR1FvRi8eKxhbaUDbbTbt0swm7E6GE/gQvHlS8+o+8+W/ctjlo64OBx3szzMwLUykMuu63s7K6tr6xWdoqb+/s7u1XDg4fTZJpxn2WyES3Q2q4FIr7KFDydqo5jUPJW+HoZuq3nrg2IlEPOE55ENOBEpFgFK103+zVe5WqW3NnIMvEK0gVCjR7la9uP2FZzBUySY3peG6KQU41Cib5pNzNDE8pG9EB71iqaMxNkM9OnZBTq/RJlGhbCslM/T2R09iYcRzazpji0Cx6U/E/r5NhdBnkQqUZcsXmi6JMEkzI9G/SF5ozlGNLKNPC3krYkGrK0KZTtiF4iy8vE79eu6q5d+fVxnWRRgmO4QTOwIMLaMAtNMEHBgN4hld4c6Tz4rw7H/PWFaeYOYI/cD5/AD3ejUw=</latexit>
Figure 1.2: Top: interference experiment with electrons. Bottom: repeating the experiment
while observing the electrons with light.
distribution is not seem to be the same as in the football-experiment! Since electrons are
not getting fractionated during the experiment, it should come through only one of the
holes; either hole 1 or hole 2. However, we don’t know which hole an electron passes
through. Interestingly, when one of the holes is closed, we get probability distribution
that is consistent with the football-experiment. We find that P1 + P2 6= P12 . If P1 = |φ1 |2
and P2 = |φ2 |2 , then P12 = |φ1 + φ2 |2 , and if we consider electrons behaving like the
water wave, we can understand the origin of the interference.
That is, “electrons are behaving like a particle as well as wave” - how and why?
Now, if we repeat the experiment, but by keeping a light source between the two
slits such that we can see if the electron reaching the detector is going through the hole
1 or the hole 2. If an electron is coming out through hole 2, then we should be seeing
a flash at the point "A" marked in the Figure 1.2. Now, without closing any holes, let
us compute the probability distribution P1 and P2 by spotting the electrons. They look
the same as we got in the case with closing one of the holes. Thus, electrons are indeed
coming out through either hole 1 or hole 2. Since we counted all the electrons, coming
through either hole 1 and hole 2 in this experiment, the total probability of finding one
electron at any point x should be the sum of P1 ( x ) and P2 ( x ). Now, we get P12 similar
Page 4
to the football-experiment! That is, no interference!

Is it possible that the light-source created some disturbance to the electrons? When
"photons" are getting reflected by the electrons, it is likely that there is some energy
transfer, which has created this difference. If we pump photons with less rate from the
light-source, i.e. dimmer light, then we note that some of the electrons coming out of
slit-1 or slit-2 are not reflected by photons, and thus not seen as flashes. Thus, it is clear
that P12 6= P1 + P2 in this experiment. If we now separately compute the probability of
electrons that are not seen as flashes (i.e. not interacted with the photons), using the
detector’s response, then we indeed see an interference pattern! How shall we explain
these observations?
Page 5

Introduction To Quantum Mechanics

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Introduction To Quantum Mechanics

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Lecture 1

Introduction to Quantum Mechanics

– Quantum Chemistry, D. A. McQuarrie

– Quantum Chemistry, I. N. Levine

– Molecular Quantum Mechanics, by P. Atkins and R. Friedman

• Memorize the equations/constants/definitions that are marked in red only

• Solve numerical and analytical problems from the reference books

1.1 Quantization of Energy

h = 6.626 × 10−34 J s (1.1)

and ν is the frequency of the electromagnetic wave.

1.2 Thought Experiment to Realise the Quantum Effect!

to the football-experiment! That is, no interference!

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