Chapter 05Vibrational Motion
P. J. Grandinetti
Chem. 4300
P. J. Grandinetti Chapter 05: Vibrational Motion
Simple Harmonic Oscillator
Simplest model for harmonic oscillator: mass attached to one end of spring while other end isheld fixed
+x-x 0
m
Mass at x = 0 corresponds to equilibrium positionx is displacement from equilibrium.Assume no friction and spring has no mass.
P. J. Grandinetti Chapter 05: Vibrational Motion
Simple Harmonic Oscillator
Pull mass and let go.
+x-x 0
m
Mass at x = 0 corresponds to equilibriumpositionx is displacement from equilibrium.Assume no friction and spring has nomass.
What happens? An oscillation.
Time for 1 complete cycle is T.How do we get and solve equation of motionfor this system?
P. J. Grandinetti Chapter 05: Vibrational Motion
Simple Harmonic OscillatorHookeโs law
For small displacements from equilibrium restoring force is F = โ๐ fxwhere ๐ f is force constant for spring.
Use Newtonโs 2nd law: F = ma = โ๐ fx
to obtain differential equation of motion: mx(t) + ๐ fx(t) = 0
Propose solution
x(t) = A cos(๐t + ๐), x(t) = A๐ sin(๐t + ๐), x(t) = โA๐2 cos(๐t + ๐)
Substitute into differential equation:(๐ f โ m๐2)A cos(๐t + ๐) = 0
Satisfy solution for all t by making m๐2 = ๐ f through definition: ๐ = ๐0 =โ๐ fโm
P. J. Grandinetti Chapter 05: Vibrational Motion
Simple Harmonic OscillatorSolution is
x(t) = A cos(๐0t + ๐)
where ๐0 โก natural oscillation frequency given by ๐ = ๐0 =โ๐ fโm
Velocity of mass isv(t) = x(t) = โ๐0A sin(๐0t + ๐)
Make x(t) and x(t) equations satisfy initial conditions of
x(t = 0) = A and x(t = 0) = 0
by setting ๐ = 0 and A = x(0) to get final solution
x(t) = x(0) cos๐0t and v(t) = โ๐0x(0) sin(๐0t)
P. J. Grandinetti Chapter 05: Vibrational Motion
Simple Harmonic Oscillator โ Other trial solutions
Instead of using x(t) = A cos(๐t + ๐) as trial solution for mx(t) + ๐ fx(t) = 0โถ Could have used
x(t) = A cos๐t + B sin๐t.
โถ Could also have used complex variables:โ replace x(t) with a complex variable, z(t),
mz(t) + ๐ fz(t) = 0
โ Make an initial guess of
z(t) = Aei(๐t+๐) or z(t) = Aei๐t + Beโi๐t
โ Obtain real solution by taking real part of complex solution, z(t).
P. J. Grandinetti Chapter 05: Vibrational Motion
Complex Variables Review
P. J. Grandinetti Chapter 05: Vibrational Motion
Complex Variables ReviewComplex variables are a mathematical tool that simplifies equations describing oscillations.Consider the 2D motion of this vector.
How would you describe this mathematically?You probably would suggest:
x(t) = r cos๐t and y(t) = r sin๐tP. J. Grandinetti Chapter 05: Vibrational Motion
Complex Variables ReviewWith complex notation we combine two equations into one
Start with x(t) = r cos๐t and y(t) = r sin๐t
First we define the square root of โ1 as
if i =โโ1 then i2 = โ1
Second we define complex variable z as
z = x + iy
x is real part and y is imaginary part of z.
Two circular motion equations become one circular motion equation
z(t) = r cos๐t + ir sin๐t
P. J. Grandinetti Chapter 05: Vibrational Motion
Complex Variables ReviewEulerโs formula
In 1748 Euler showed that ei๐ = cos ๐ + i sin ๐ Eulerโs formula
With Eulerโs formula z(t) = r cos๐t + ir sin๐t becomes z(t) = rei๐t
Calculate the product (cos๐at + i sin๐at)(cos๐bt + i sin๐bt).
(cos๐at+ i sin๐at)(cos๐bt+ i sin๐bt) = cos๐at cos๐bt+ i cos๐at sin๐bt+ i sin๐at cos๐btโsin๐at sin๐bt
2 cos ๐ cos๐ = cos(๐ โ ๐) + cos(๐ + ๐) 2 sin ๐ sin๐ = cos(๐ โ ๐) โ cos(๐ + ๐)2 sin ๐ cos๐ = sin(๐ + ๐) + sin(๐ โ ๐) 2 cos ๐ sin๐ = sin(๐ + ๐) โ sin(๐ โ ๐)
(cos๐at + i sin๐at)(cos๐bt + i sin๐bt) = cos(๐a + ๐b)t + i sin(๐a + ๐b)t
Using Eulerโs formula:(cos๐at + i sin๐at)(cos๐bt + i sin๐bt) = ei๐atei๐bt = ei(๐a+๐b)t = cos(๐a + ๐b)t + i sin(๐a + ๐b)t
P. J. Grandinetti Chapter 05: Vibrational Motion
Complex Variables Review
Any complex number can be written in the form
z = x + iy = |z|ei๐
where |z| is the magnitude of the complex number
|z| = โx2 + y2
and ๐ is the argument of the complex number
tan ๐ = yโx
P. J. Grandinetti Chapter 05: Vibrational Motion
Complex Variables ReviewComplex Conjugate
Complex conjugate, zโ, of z is obtained by changing sign of imaginary part
if z = x + iy then zโ = x โ iy
if z = 1 + 4i4 โ 5i
then zโ = 1 โ 4i4 + 5i
if z = 1 + ia4 โ ib
then zโ = 1 โ iaโ4 + ibโ
.
Related identitiesโถ |z| = โ
zzโ, since
zzโ = (x + iy)(x โ iy) = x2 + iyx โ ixy + y2 = x2 + y2 = |z|2โถ (z1z2z3 โฏ)โ = zโ1zโ2zโ3 โฏ
P. J. Grandinetti Chapter 05: Vibrational Motion
Energy of simple harmonic oscillator
P. J. Grandinetti Chapter 05: Vibrational Motion
Energy of simple harmonic oscillatorTotal energy of simple harmonic oscillator is sum of kinetic and potential energy of mass andspring.
Kinetic energy is given by
K = 12
mv2, or K =p2
2m
Potential energy is energy stored in spring and equal to work done in extending andcompressing spring,
V(x) = โโซx
0F(xโฒ)dxโฒ = โซ
x
0๐ fxโฒdxโฒ = 1
2๐ fx2
Expression above is work associated with extending spring.
For work in compressing spring just change integral limits to โx to 0 (get same result).
P. J. Grandinetti Chapter 05: Vibrational Motion
Energy of simple harmonic oscillatorPotential energy is given by
V(x) = 12๐ fx2
V(x)
0x
P. J. Grandinetti Chapter 05: Vibrational Motion
Energy of simple harmonic oscillator
Although both K and V are time dependent during harmonic motion the total energy,E = K + V, remains constant.
E = 12
mv2(t) + 12๐ fx2(t) or E =
p2(t)2m
+ 12๐ fx2(t)
EnergyKinetic Energy
Potential EnergyTotal Energy
P. J. Grandinetti Chapter 05: Vibrational Motion
Energy of simple harmonic oscillatorSubstitute equation of motion into energy expression
E = 12
mv2(t) + 12๐ fx2(t) = 1
2m๐2
0x2(0) sin2(๐0t) + 12๐ fx2(0) cos2 ๐0t
Recall that ๐ f = m๐20 so
E = 12
m๐20x2(0)
[sin2(๐0t) + cos2 ๐0t
]= 1
2m๐2
0x2(0)
Solve for initial amplitude, x(0), in terms of energy
x(0) = 1๐0
โ2Em
and rewrite oscillation as
x(t) = x(0) cos๐0t =โ
2E๐2
0mcos๐0t and v(t) = โ๐0x(0) sin(๐0t) = โ
โ2Em
sin๐0t
P. J. Grandinetti Chapter 05: Vibrational Motion
Simple Harmonic Oscillator - Phase Space Trajectory
x(t) = x(0) cos๐0t =โ
2E๐2
0mcos๐0t and v(t) = โ๐0x(0) sin(๐0t) = โ
โ2Em
sin๐0t
State of oscillator specified by point in phase spaceE = constant means oscillator state always lies on ellipse
x2
2Eโ๐ f+ v2
2Eโm= 1
Trajectory moves in clockwise direction.Trajectories with different E can never cross.
P. J. Grandinetti Chapter 05: Vibrational Motion
Position probability distribution for harmonic oscillator
P. J. Grandinetti Chapter 05: Vibrational Motion
Position probability distribution for harmonic oscillatorScale x(t) by initial amplitude x(0), to obtain a function, y(t), that oscillates between y = โ1and y = +1
y(t) = x(t)โx(0) = cos๐0tCalculate normalized probability density, p(y), for finding the mass at any scaled positionbetween y = ยฑ1.Probability of finding mass in interval dy at given y is proportional to time spent in dy interval,
p(y) dy = b dt = b dtdydy
= b dy dtdy
= by
dy
b โก proportionality constant, and y โก speed at a given yUse derivative of y(t)
y(t) = โ๐0 sin๐0tto obtain
p(y) = by(t)
= bโ๐0 sin๐0t
= bโ๐0(1 โ cos2 ๐0t)1โ2
= bโ๐0(1 โ y2)1โ2
P. J. Grandinetti Chapter 05: Vibrational Motion
Position probability distribution for harmonic oscillator
p(y) = bโ๐0(1 โ y2)1โ2
Normalizing probability distribution gives
p(y) = 1๐(1 โ y2)1โ2
+x-x 0
m-1.0 -0.5 0.0 0.5 1.0
2
0
4
6
8
10
Mass spends majority of time at maximumexcursions, that is, turning points where velocity isslowest and changes sign.
P. J. Grandinetti Chapter 05: Vibrational Motion
Diatomic molecule vibration as Harmonic oscillator
P. J. Grandinetti Chapter 05: Vibrational Motion
Diatomic molecule vibration as Harmonic oscillator
Dashed line is harmonic oscillator potential. Solid line is Morse potential.V(r) has minimum at reโwhere restoring force is zero.V(r) causes repulsive force at r < re and attractive force at r > re.V(r) increases steeply at r < re but levels out to constant at r > re.At r โ โ there is no attractive force as V(r) has a slope of zero.
P. J. Grandinetti Chapter 05: Vibrational Motion
Diatomic molecule vibration as Harmonic oscillatorTaylor series expansion of V(r) about equilibrium bond length, r = re, gives
V(r) โ V(re) +๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ>
0dV(re)
dr(r โ re) +
12!
d2V(re)dr2 (r โ re)2 +
13!
d3V(re)dr3 (r โ re)3 +โฏ
V(re) is the potential energy at equilibrium bond length.1st-order term is zero since no restoring force, F = โdV(re)โdr, at r = re
Stop expansion at the 3rd-order term and define 2 constants
๐ f =d2V(re)
dr2 and ๐พf =d3V(re)
dr3
and write potential expansion as
V(r) โ V(re) โ12๐ f(r โ re)2 +
16๐พf(r โ re)3 +โฏ
For small displacements drop 3rd-order term and potential looks like simple harmonic oscillator.For slightly larger displacements keep 3rd-order term to account for vibration anharmonicity.
P. J. Grandinetti Chapter 05: Vibrational Motion
Diatomic molecule vibration equations of motion
Make harmonic oscillator approximation taking force on m1 and m2 as
F1 = โ๐ f(r1 โ r2 + re) and F2 = โ๐ f(r2 โ r1 โ re)
Equations of motion are 2 coupled differential equations:
m1d2r1
dt2= ๐ f(r2 โ r1 โ re) and m2
d2r2
dt2= โ๐ f(r2 โ r1 โ re)
Transform to center of mass frame: M = m1 + m2 and R = 1M (m1r1 + m1r2)
Obtain 2 uncoupled differential equations,
M d2Rdt2
= 0, and ๐d2ฮrdt2
= โ๐ fฮr
ฮr = r2 โ r1 โ re and ๐ is the reduced mass given by 1๐
= 1m1
+ 1m2
P. J. Grandinetti Chapter 05: Vibrational Motion
Diatomic molecule vibration equations of motionDifferential equation of motion describing the vibration
๐dฮr2(t)
dt2 + ๐ fฮr(t) = 0
Same differential equation of motion as simple harmonic oscillator.
Solutions takes the same form,
ฮr(t) = ฮr(0) cos๐0t where ๐0 =โ๐ fโ๐
In spectroscopy vibrational frequencies are given in terms of the spectroscopic wavenumber,
๏ฟฝ๏ฟฝ =๐0
2๐c0=
โ๐ fโ๐
2๐c0, rearranges to ๐ f = ๐
(2๐c0๏ฟฝ๏ฟฝ
)2
P. J. Grandinetti Chapter 05: Vibrational Motion
Force constants for selected diatomic molecules
๐ f = ๐(2๐c0๏ฟฝ๏ฟฝ
)2
Bond ๐ f/(N/m) ๐โ10โ28 kg ๏ฟฝ๏ฟฝ/cmโ1 Bond length/pmHโH 570 8.367664 4401 74.1DโD 527 16.72247 2990 74.1
Hโ35Cl 478 16.26652 2886 127.5Hโ79Br 408 16.52430 2630 141.4Hโ127I 291 16.60347 2230 160.9
35Clโ35Cl 319 290.3357 554 198.879Brโ79Br 240 655.2349 323 228.4127Iโ127I 170 1053.649 213 266.7
16O=16O 1142 132.8009 1556 120.714Nโก14N 2243 116.2633 2331 109.412Cโก16O 1857 113.8500 2143 112.814N=16O 1550 123.9830 1876 115.123Naโ35Cl 117 230.3282 378 236.139Kโ35Cl 84 306.0237 278 266.7
23Naโ23Na 17 190.8770 158 307.8
P. J. Grandinetti Chapter 05: Vibrational Motion
Coupled Harmonic Oscillators and Normal Modes
P. J. Grandinetti Chapter 05: Vibrational Motion
Two coupled oscillators constrained to move in one dimension
m m
+x1-x1 0 +x2-x2 0
2 equal masses connected with 3 springs with force constants ๐ 1 and ๐ 2.3 springs are at equilibrium lengths when x1 = x2 = 0.Middle spring is also at equilibrium length whenever x2 = x1.Restoring force acting on left mass: F1 = โ๐ 1x1 + ๐ 2(x2 โ x1)Restoring force acting on right mass: F2 = โ๐ 1x2 โ ๐ 2(x2 โ x1)Coupled differential equations of motion for each mass:
mx1 + (๐ 1 + ๐ 2)x1 โ ๐ 2x2 = 0 and mx2 โ ๐ 2x1 + (๐ 1 + ๐ 2)x2 = 0
P. J. Grandinetti Chapter 05: Vibrational Motion
Two coupled oscillators: Normal ModesCoupled differential equations: mx1 + (๐ 1 + ๐ 2)x1 โ ๐ 2x2 = 0 and mx2 โ ๐ 2x1 + (๐ 1 + ๐ 2)x2 = 0
Uncoupled by coordinate transformation: ๐1 = x1 + x2 and ๐2 = x1 โ x2
๐1 and ๐2 are called normal mode coordinates
Gives 2 uncoupled equations: m๐1 + (๐ 1 + 2๐ 2)๐1 = 0 and m๐2 + ๐ 1๐2 = 0
Substitute 2 proposed solutions: ๐1(t) = A1 cos(๐1t + ๐1) and ๐2(t) = A2 cos(๐2t + ๐2)
Obtain:((๐ 1 + 2๐ 2) โ m๐2
1)
A1 cos(๐1t + ๐1) = 0 and(๐ 1 โ m๐2
2)
A2 cos(๐2t + ๐2) = 0
Equations true for all values of t if: (๐ 1 + 2๐ 2) = m๐21 and ๐ 1 = m๐2
2
yields 2 normal mode frequencies: ๐1 =โ(๐ 1 + 2๐ 2)โm and ๐2 =
โ๐ 1โm Note: ๐1 > ๐2
Normal mode is collective oscillation where all masses move with same oscillation frequency.
P. J. Grandinetti Chapter 05: Vibrational Motion
Two coupled oscillators: Normal Modes
Imposing initial conditions:
๐1(0) = x1(0) + x2(0) and ๐2(0) = x1(0) โ x2(0), and ๏ฟฝ๏ฟฝ1(0) = ๏ฟฝ๏ฟฝ2(0) = 0
on solutions: ๐1(t) = A1 cos(๐1t + ๐1) and ๐2(t) = A2 cos(๐2t + ๐2)gives:
๐1 = ๐2 = 0 and A1 = ๐1(0) and A2 = ๐2(0)
๐1(t) = ๐1(0) cos(๐1t) and ๐2(t) = ๐2(0) cos(๐2t)
Converting normal mode coordinates back to original coordinates:
x1(t) =12
[๐2(0) cos(๐2t) + ๐1(0) cos(๐1t)
]and x2(t) =
12
[๐2(0) cos(๐2t) โ ๐1(0) cos(๐1t)
]Oscillation of each mass is linear combination of two normal mode oscillations.
P. J. Grandinetti Chapter 05: Vibrational Motion
Two coupled oscillators: Normal ModesConsider two cases where only one normal mode is active:
๐2(0) = 0 or ๐1(0) = 0
x1(t) = 12๐1(0) cos(๐1t)
x2(t) = โ 12๐1(0) cos(๐1t)
โซโชโฌโชโญ out-of-phase,x1(t) = 1
2๐2(0) cos(๐2t)
x2(t) = 12๐2(0) cos(๐2t)
โซโชโฌโชโญ in-phase.
m m
m m
out of phase normal mode
m m
in phase normal mode
m m
m
m m
m
All motion in this system can be decomposed into linear combination of these two normal modes.P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysisConsider a harder problem
m1 m2
+x1-x1 0 +x2-x2 0
Both masses and all 3 spring constants are different.Simple coordinate transformation ๐1 = x1 + x2 and ๐2 = x1 โ x2 will not transform probleminto uncoupled differential equations.Need systematic approach for determining coordinate transformation (normal modes) thattransform coupled linear differential equations into uncoupled differential equations.
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis
m1 m2
+x1-x1 0 +x2-x2 0
Define mass-weighted coordinates: q1 = m1โ21 x1 and q2 = m1โ2
2 x2Coupled differential equations are
q1 +(๐ 1 + ๐ 2)
m1q1 โ
๐ 2
(m2m1)1โ2q2 = 0 and q2 โ
๐ 2
(m2m1)1โ2q1 โ
(๐ 3 โ ๐ 2)m2
q2 = 0
In matrix form:
โกโขโขโฃq1
q2
โคโฅโฅโฆโโโ
q
+
โกโขโขโขโขโขโฃ
(๐ 1 + ๐ 2)m1
โ๐ 2
(m2m1)1โ2
โ๐ 2
(m2m1)1โ2
(๐ 3 + ๐ 2)m2
โคโฅโฅโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
K
โกโขโขโฃq1
q2
โคโฅโฅโฆโโโ
q
= 0
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysisAny coupled harmonic oscillator problem can be written in form: q + Kq = 0
K is a square n ร n real symmetric (i.e., K12 = K21) matrix, q and q are n ร 1 matrices.Similarity transformation of real n ร n symmetric matrix into diagonal matrix, ๐ฒ.
LT KL =
โกโขโขโขโฃl11 l21 โฆ ln1l12 l22 โฆ ln2โฎ โฎ โฑ โฎl1n l2n โฆ lnn
โคโฅโฅโฅโฆโกโขโขโขโฃ
K11 K12 โฆ K1nK21 K22 โฆ K2nโฎ โฎ โฑ โฎ
Kn1 Kn2 โฆ Knn
โคโฅโฅโฅโฆโกโขโขโขโฃ
l11 l12 โฆ l1nl21 l22 โฆ l2nโฎ โฎ โฑ โฎln1 ln2 โฆ lnn
โคโฅโฅโฅโฆ =โกโขโขโขโฃ
๐1 0 โฆ 00 ๐2 โฆ 0โฎ โฎ โฑ โฎ0 0 โฆ ๐n
โคโฅโฅโฅโฆ = ๐ฒ
โถ Eigenvalues, ๐i, of K along diagonal of ๐ฒ.โถ Eigenvectors, li, of K along columns of L and along rows of LT .โถ L is orthogonal matrix: product with its transpose, LT , is identity matrix, 1,
LLT =
โกโขโขโขโฃl11 l12 โฆ l1nl21 l22 โฆ l2nโฎ โฎ โฑ โฎln1 ln2 โฆ lnn
โคโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
L
โกโขโขโขโฃl11 l21 โฆ ln1l12 l22 โฆ ln2โฎ โฎ โฑ โฎl1n l2n โฆ lnn
โคโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
LT
=
โกโขโขโขโฃ1 0 โฆ 00 1 โฆ 0โฎ โฎ โฑ โฎ0 0 โฆ 1
โคโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโ
1
= 1
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysisInsert identity matrix as 1 = LLT before and after K in matrix form of equations of motion:
q + Kq = q + (LLT )โโโ
1
K (LLT )โโโ
1
q = q + L (LTKL)โโโ
๐ฒ
(LTq) = 0
Multiplying both sides by LT , regroup, and define new matrix variables:
LT
โโโโโq + L (LTKL)โโโ
๐ฒ
LTqโโโโโ = LT q
โโโQ
+ (LTKL)โโโ
๐ฒ
(LT q)โโโ
Q
= Q + ๐ฒ Q = 0
Q = LT q is linear transformation of q into Q, i.e., normal mode coordinatesDifferential equations in Q and ๐ฒ are uncoupled for each normal mode coordinate: Qi + ๐iQi = 0Substitute in proposed solutions: Qi(t) = Ai cos(๐it+๐i) gives (๐i โ๐2
i ) cos(๐it+๐i) = 0
Identify the ith normal mode frequency as ๐i =โ๐i
With initial conditions, solutions become Qi(t) = Qi(0) cos(๐it
)P. J. Grandinetti Chapter 05: Vibrational Motion
How do we determine eigenvalues, ๐i, and the eigenvectors, li, from K?ith row in L is li eigenvector for ๐i eigenvalue.
Kli =โกโขโขโขโฃ
K11 K12 โฆ K1nK21 K22 โฆ K2nโฎ โฎ โฑ โฎ
Kn1 Kn2 โฆ Knn
โคโฅโฅโฅโฆโกโขโขโขโฃ
li1li2โฎlin
โคโฅโฅโฅโฆ = ๐ili = ๐i
โกโขโขโขโฃli1li2โฎlin
โคโฅโฅโฅโฆ = ๐i
โกโขโขโขโฃ1 0 โฆ 00 1 โฆ 0โฎ โฎ โฑ โฎ0 0 โฆ 1
โคโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโ
1
โกโขโขโขโฃli1li2โฎlin
โคโฅโฅโฅโฆโโโโโโโโโ
โกโขโขโขโฃK11 K12 โฆ K1nK21 K22 โฆ K2nโฎ โฎ โฑ โฎ
Kn1 Kn2 โฆ Knn
โคโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
K
โ๐i
โกโขโขโขโฃ1 0 โฆ 00 1 โฆ 0โฎ โฎ โฑ โฎ0 0 โฆ 1
โคโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโ
1
โโโโโโโโโ
โกโขโขโขโฃli1li2โฎlin
โคโฅโฅโฅโฆโโโ
li
= 0
Compactly written as(K โ ๐i1) li = 0
Encountered same problem when diagonalizing moment of inertia tensor to determine PAS componentsand orientation.
P. J. Grandinetti Chapter 05: Vibrational Motion
How do we determine eigenvalues, ๐i, and the eigenvectors, li, from K?
Obtain eigenvalues by expanding determinant
|K โ ๐i1| = 0
to get nth order polynomial equation in ๐ whose roots are eigenvalues.
Substitute each eigenvalue back into (K โ ๐i1) li = 0 to get corresponding eigenvector.
Determining eigenvalues and eigenvectors of a matrix is usually done numerically. Softwarepackages utilizing various algorithms for matrix diagonalization are available in various problemsolving environments such as MatLab, Mathematica, or Python notebooks.
P. J. Grandinetti Chapter 05: Vibrational Motion
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysisBack to our original problem
โกโขโขโฃq1
q2
โคโฅโฅโฆโโโ
q
+
โกโขโขโขโขโขโฃ
(๐ 1 + ๐ 2)m1
โ๐ 2
(m2m1)1โ2
โ๐ 2
(m2m1)1โ2
(๐ 3 + ๐ 2)m2
โคโฅโฅโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
K
โกโขโขโฃq1
q2
โคโฅโฅโฆโโโ
q
= 0
To solve this problem we willdetermine eigenvalues, ๐i and eigenvectors, li, of Kobtain normal mode frequencies from ๐i =
โ๐i
obtain relationship between mass-weighted and normal-mode coordinates from Q = LTq
To make solution more manageable, only illustrate the case where m1 = m2 = m and ๐ 3 = ๐ 1.
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis - Find the Eigenvalues
Obtain eigenvalues by solving the determinant,|||||||||๐ 1 + ๐ 2
mโ ๐ โ
๐ 2m
โ๐ 2m
๐ 1 + ๐ 2m
โ ๐
|||||||||=(๐ 1 + ๐ 2
mโ ๐
)(๐ 1 + ๐ 2
mโ ๐
)โ
๐ 22
m2 = 0
obtaining๐2 = ๐ =
๐ 1 + ๐ 2 ยฑ ๐ 2m
๐1 = (๐ 1 + 2๐ 2)โm and ๐2 = ๐ 1โm
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis - Find the EigenvectorsObtain first eigenvector, associated with ๐1 = (๐ 1 + 2๐ 2)โm, by expandingโกโขโขโฃ
(๐ 1 + ๐ 2)โm โ ๐1 โ๐ 2โm
โ๐ 2โm (๐ 1 + ๐ 2)โm โ ๐1
โคโฅโฅโฆโกโขโขโฃ
l11
l12
โคโฅโฅโฆ = 0,
to get 2 identical equations:((๐ 1 + ๐ 2)โm โ ๐1
)l11 โ (๐ 2โm)l12 = 0, and โ (๐ 2โm)l11 +
((๐ 1 + ๐ 2)โm โ ๐1
)l12 = 0,
which simplify to l11 = โl12, i.e. two elements have equal magnitude and opposite sign.
l1 =[
l11l12
]= b
[1โ1
]where b is some unknown constant.
Insisting that l1 be normalized, i.e.,โ
l211 + l212 = 1, gives b = 1โโ
2 and our 1st eigenvector is:
l1 =[
l11l12
]=
[1โ
โ2
โ1โโ
2
]P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis - Find the EigenvectorsSimilarly, second eigenvector, associated with ๐2 = ๐ 1โm, is given by
l2 =โกโขโขโฃ
l21
l22
โคโฅโฅโฆ =โกโขโขโฃ
1โโ
2
1โโ
2
โคโฅโฅโฆTaking these two results together, we construct the eigenvector matrix
L =[
l11 l21l12 l22
]=โกโขโขโฃ
1โโ
2 1โโ
2
โ1โโ
2 1โโ
2
โคโฅโฅโฆFinally, we obtain solutions, in terms of the mass-weighted coordinates, as
q = LQ =โกโขโขโฃ
q1
q2
โคโฅโฅโฆ =โกโขโขโฃ
1โโ
2 1โโ
2
โ1โโ
2 1โโ
2
โคโฅโฅโฆโกโขโขโฃ
Q1(0) cos๐1t
Q2(0) cos๐2t
โคโฅโฅโฆP. J. Grandinetti Chapter 05: Vibrational Motion
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P. J. Grandinetti Chapter 05: Vibrational Motion
Polyatomic Molecule Vibrations
P. J. Grandinetti Chapter 05: Vibrational Motion
Polyatomic Molecule VibrationsNormal mode analysis of molecule with N atoms
Define each atomโs displacement coordinates in PAS of moleculeโs moment of inertia tensor withcenter of mass at origin.For example, for water molecule define
105ยฐ
a
b
๐1 = aO โ aO,e, ๐2 = bO โ bO,e, ๐3 = cO โ cO,e,๐4 = aH1
โ aH1,e, ๐5 = bH1โ bH1,e, ๐6 = cH1
โ cH1,e,๐7 = aH2
โ aH2,e, ๐8 = bH2โ bH2,e, ๐9 = cH2
โ cH2,e,
subscript e represents equilibrium coordinate.โถ Further define mass-weighted displacement coordinates, q1,โฆ , q3N , e.g.,
qi = m1โ2i ๐i where
m1 = m2 = m3 = mO, m4 = m5 = m6 = mH , and m7 = m8 = m9 = mH .Derive equations of motion from kinetic and potential energy
ddt
(๐K(q1,โฆ , q3N)
๐q
)+
๐V(q1,โฆ , q3N)๐qi
= 0
P. J. Grandinetti Chapter 05: Vibrational Motion
Polyatomic Molecule VibrationsKinetic and Potential Energy in mass-weighted coordinates
Kinetic energy becomes
K = 12
3Nโi=1
(dqidt
)2= 1
2qT q where qT =
[dq1dt
,โฆ ,dq3N
dt
]and q is its transpose
Potential energy expanded as Taylor-series expansion
V(q) = V(0) +3Nโi=1 ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ๏ฟฝ*
0(๐V(0)๐qi
)qi + 1
2
3Nโi=1
3Nโk=1
(๐2V(0)๐qi๐qk
)qiqk +โฏ
Rewriting as
V(q) โ V(0) + 12
qT q where qT =[q1,โฆ , q3N
], and q is its transpose
where is 3N ร 3N matrix with elements given by
i,k =(๐2V(0)๐qi๐qk
)P. J. Grandinetti Chapter 05: Vibrational Motion
Polyatomic Molecule VibrationsNormal mode analysis of molecule with N atoms
Derive equations of motion from kinetic and potential energy
ddt
(๐K(q1,โฆ , q3N)
๐q
)+
๐V(q1,โฆ , q3N)๐qi
= 0
and obtain a set of 3N coupled differential equations (in matrix notation),
q + q = 0As before, heart of the problem is determining eigenvalues, ๐i, and eigenvectors, li of .Orthogonal eigenvector matrix, L, transforms problem into 3N uncoupled differential equations,
q + q = q + (LLT )(LLT )q = 0 โถ LT q + (LTL) (LTq) = Q + ๐ฒQ = 0
โถ solutions: Qi(t) = Qi(0) cos(๐it)โถ normal mode frequencies: ๐i =
โ๐i
โถ normal mode coordinates: Q = LTqNormal modes with identical frequencies are called degenerate modes.
P. J. Grandinetti Chapter 05: Vibrational Motion
Polyatomic Molecule VibrationsNormal mode analysis of molecule with N atoms
Since translational and rotational coordinates are included, 5 or 6 normal modefrequencies, depending on whether molecule is linear or not, respectively, will be zero.Potential and kinetic energy in terms of the vibrational normal modes coordinates are
V โ Ve โ12
QT๐ฒQ = 12
3Nโ6โi
๐iQ2i , and K = 1
2QTQ = 1
2
3Nโ6โi
Q2i .
Keep in mind that approximations were made along the way.โถ Ignored anharmonic (3rd and higher order) terms ignored in Taylor-series expansion of V(q).
Can still use matrix, but anharmonicities cause small couplings between the โnormalmodes.โ
โถ Coordinate system fixed on molecule, i.e., PAS of moment of inertia tensor, is a rotatingframe. We neglected fictitious forces of such a frame. Coriolis forces will cause smallcouplings between the normal modes.
Primary task: obtain matrix and find its eigenvalues and eigenvectors.P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis of diatomic molecule
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis of diatomic molecule
a
b Define displacements in PAS of its moment of inertia tensor.
๐1 = aA โ aA,e, ๐2 = bA โ bA,e = 0, ๐3 = cA โ cA,e = 0,๐4 = aB โ aB,e, ๐5 = bB โ bB,e = 0, ๐6 = cB โ cB,e = 0,
From 6 displacement coordinates, define mass-weighted coordinates,qi = m1โ2
i ๐i, where m1 = m2 = m3 = mA, and m4 = m5 = m6 = mB.
Since ฮr = r โ re = ๐4 โ ๐1 = q1โm1โ21 โ q4โm1โ2
4 we obtain potential energy function
V โ Ve โ12๐ f(r โ re)2 = 1
2๐ f
(q1
m1โ21
โq4
m1โ24
)2
= 12๐ f
(q2
1m1
โ2q1q4
(m1m4)1โ2+
q24
m4
)Identify non-zero matrix elements of as
11 = ๐ fโm1, and 44 = ๐ fโm4, and 14 = โ๐ fโ(m1m4
)1โ2
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis of diatomic moleculeEquations of motion in matrix form is
โกโขโขโขโขโขโขโขโขโขโขโขโขโขโฃ
q1
q2
q3
q4
q5
q6
โคโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฆโโโ
q
+
โกโขโขโขโขโขโขโขโขโขโขโขโขโขโขโขโขโฃ
๐ f
m10 0 โ
๐ f(m1m4
)1โ20 0
0 0 0 0 0 0
0 0 0 0 0 0
โ๐ f(
m1m4)1โ2
0 0๐ f
m40 0
0 0 0 0 0 0
0 0 0 0 0 0
โคโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฆโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโโ
โกโขโขโขโขโขโขโขโขโขโขโขโขโขโฃ
q1
q2
q3
q4
q5
q6
โคโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฅโฆโโโ
q
= 0
Note: Four equations are already uncoupled and have eigenvalues of ๐i = 0.
P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis of diatomic moleculeRemaining equations of motion are[
q1q4
]+โกโขโขโฃ
๐ fโm1 โ๐ fโ(m1m4
)1โ2
โ๐ fโ(m1m4
)1โ2 ๐ fโm4
โคโฅโฅโฆ[
q1q4
]= 0
Get eigenvalues from solving|||||||๐ fโm1 โ ๐ โ๐ fโ
(m1m4
)1โ2
โ๐ fโ(m1m4
)1โ2 ๐ fโm4 โ ๐
||||||| = (๐ fโm1 โ ๐)(๐ fโm4 โ ๐) โ ๐ 2f โ
(m1m4
)= 0
gives ๐ = 0 and๐ f๐
where 1๐
= 1m1
+ 1m4
=m1 + m4
m1m4= M
m1m4, or ๐ = (m1m4)โM,
๐ is the reduced mass, and M = m1 + m4 is the total mass.5 out of 6 eigenvalues are zeroโassociated with 3 translational and 2 rotational degrees offreedom.1 out of 6 degrees of freedom is associated with vibration with ๐1 =
โ๐ fโ๐, and normal mode
solution Q1(t) = Q1(0) cos(๐1t
)P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis of diatomic molecule
Turning to normal mode eigenvectors. If we substitute the eigenvalue ๐1 = ๐ fโ๐ into
( โ ๐11)l1 =
โกโขโขโขโฃ๐ fโm1 โ ๐1 โ๐ fโ
(m1m4
)1โ2
โ๐ fโ(m1m4
)1โ2 ๐ fโm4 โ ๐1
โคโฅโฅโฅโฆโกโขโขโฃ
l11
l14
โคโฅโฅโฆ = 0,
we obtain two equivalent equations, which simplify to l11 = โ(m4โm1
)1โ2 l14Write eigenvector as
l1 =โกโขโขโฃ
l11
l14
โคโฅโฅโฆ = bโกโขโขโฃโ(m4โm1
)1โ2
1
โคโฅโฅโฆ โถ l1 =
โกโขโขโขโฃ(๐โm1
)1โ2
โ(๐โm4
)1โ2
โคโฅโฅโฅโฆwhere b =
(m4โM
)1โ2 after normalization.
Same approach gives
l2 =
โกโขโขโขโฃ(๐โm4
)1โ2
(๐โm1
)1โ2
โคโฅโฅโฅโฆP. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis of diatomic moleculeBring eigenvectors together to create transformation between mass-weighted and normalcoordinates:
Q = LTq =โกโขโขโฃ
Q1
Q4
โคโฅโฅโฆ =โกโขโขโขโขโขโฃ
(๐
m1
)1โ2โ(
๐m4
)1โ2
(๐
m4
)1โ2 (๐
m1
)1โ2
โคโฅโฅโฅโฅโฅโฆโกโขโขโฃ
q1
q4
โคโฅโฅโฆThe Q1 coordinate expands to
Q1 = (๐)1โ2 ( q1โm1โ21
โโโ๐1
โ q4โm1โ24
โโโ๐4
)= (๐)1โ2 ( ๐1 โ ๐4
โโโฮr
)= (๐)1โ2 ฮr
Rearranging gives vibrational motion solution:
ฮr(t) = (๐)โ1โ2 Q1(t) = (๐)โ1โ2 Q1(0) cos(๐1t
)P. J. Grandinetti Chapter 05: Vibrational Motion
Normal mode analysis of diatomic moleculeQ4 normal mode (with ๐4 = 0) can be expanded as
Q4 = (๐)1โ2(
q1โm1โ24 + q4โm1โ2
1
)= 1
M1โ2
(m1๐1 + m4๐4
)= 1
M1โ2
(mA(aA โ aA,e) + mB(aB โ aB,e)
)Recalling center of mass along the a axis,
aCOM = (mAaA + mBaB)โM and aCOM,e = (mAaA,e + mBaB,e)โM = 0
where center of mass when atoms are at equilibrium coordinates is zero, gives
Q4 = M1โ2
(mAaA + mBaB
)M
= M1โ2aCOM
Since ๐4 = 0, equation of motion is Q4 = 0
initial condition of aCOM = Q4 = 0 means aCOM cannot change in time.
๐i = 0 for 5 normal modes associated with translation and rotation, so no change in center ofmass or PAS orientation as molecule vibrates.
P. J. Grandinetti Chapter 05: Vibrational Motion
Web Videos
Web Video Link: Vibration of Polyatomic MoleculesWeb Links: Crash Course Physics: Simple Harmonic Motion
P. J. Grandinetti Chapter 05: Vibrational Motion
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