Aide-mémoire OS

Introduction Experimental methods

Spectroscopy can help us to know: Basic components of an abs experiments
• Energy level • Source: Ideally continuum radiation.
• Concentration or abundances of species • Cell: Containing sample, must have windows.
• Structure
• Dispersing element: Split up the radiation.
• Dynamics
• Detector: Signal ∝ intensity of the particular wavelength failing on it.
Abs and Emi spectro
Rate: Source of radiation
• Total absorption rate: W = N Bρ
′ ′
• Total emission rate: W = N (A + Bρ)
 
8πhc 1
′
Planck black body: p(λ) = −1
• Net absorption rate: Wnet = (N − N )Bρ λ5 eβhν
2.9e − 3
– N ≡ No. of molecules in lower state Wien’s deplacement law: λmax =
′ T
– N ≡ No. of molecule in upper state
Stefan-Boltzmann law (total power emitted): ε = sS−B T 4
– B ≡ Einstein coef for stimulated abs
– A ≡ Einstein coef for stimulated emi
– ρ ≡ Energy density • ε ≡ total radiative power per unit of area
Light equation: • sS−B ≡ Stephan-Boltzmann constant, 5, 67e − 8W m2 K−4
Celerity: c = λν Black body radiation: Laser properties:
1 
Wavenumber: ν̃ = ω̃ = in cm−1
 • Monochromatic
(−) Low power
λ • Collimated beam
Energy: hν = hcω̃ (−) Uncollimated
• Coherent
(−) Limited spectral range • High power
Broadening
(−) Lack of time resolution • Pulsed
ν ν Free electron laser:
νreceding = and νapproaching = Synchrotron radiation properties:
1 + sc 1− s
c (+) Wide wavelength coverage
2ν 2kB T ln(2) 1/2
  • High Brightness (Highly collimated)
δν = (+) High spectral brightness
c m • Wide energy spectrum (−) Very large and expensive
ℏ
δE = = hcδ ω̃ • Tunable X-ray sources:
τ
(−) Fixed frequency
1 • Highly polarised
∆ν =
2πτ (−) Low power
• Emitted in very short pulses
(−) Non-directional
Beer-Lambert law: A = ln (I0 I) εcl
Dispersing elements
• A ≡ Absorbance Consists of glass or ceramic plate.
• l ≡ path length in [cm] Constructive interferance: nλ = d(sin(θ) − sin(ϕ))
• c ≡ concentration in mol dm−3
 
Wide angular separation if d ≃ λ
• ε ≡ coef molar abs in dm mol−1 cm−1
 3 
• Monochromator Only narrow range of λ to reach detector.
• Polychromator Broad range of wavelength can be analsyed.
κ
ε=
ln(10)
I = I0 e−εcl or I = I0 e−σN l FT techniques: (with IR), based on Michelson interferometers, wavenumber in signal.
(+) All light comes through to detector.
N1 g1 −β∆E
Boltzmann distribution law: N0
= g0
e (+) Very high resolution
 Detectors Rotational energy levels of diatomic molecules
Device that converts radiation into an electric current.
PMT: Photoelectric effect to generate electrical signal. Very high sensitivity, fragile, expensive,
susceptible to dark current. Ej = hcBJ(J + 1) in [J]
Photodiode: Conducts electricity when struck by photons. Easy to manufacture, not very F (J) = BJ(J + 1) in cm−1
 
sensitive.
ℏ
Charge-coupled device: 2D array of small photodiode detectors. in cm−1
 
B=
IR detector (MCT); Pitential difference changes when exposed to IR. 4πcI
Microwave detectors: Crystal diode with SC.
Indirect method.
Absorption methode: To have a rotational spectrum, molecule must have a permanent dipole moment (be polar).
(+) Simplicity • ∆J = +1 Abs
(+) Enables direct calculation of concentration
• ∆J = −1 Emi
(−) Abs have low sensitivity.
(−) Sensitive to instrumental noise. For an abs, wavenumber: ω̃ = 2B(J + 1), so separation between 2 lines is 2B
NJ gj −βEj
Cavity abs methods Boltzmann distribution: N0
= g0
e
− τt
q
kB T
Cavity ring-down spectro Light intensity: I(t) = I0 e Jmax = 2hcB
− 21
τ = − c lnℓ R ≃ c(1−R)
ℓ q
I
 
t r= (Typically Å
Light intensity if absorbing substance in cavity: I(t) = I0 e− τ −αct with α = ε[absorber] ≡ σN µ

(+) Higher sensitivity Non-rigid rotors

(+) Insensitive to pulse to pulse fluctuation
(−) Can be hard to obtain sufficiently high R mirror F (J) = BJ(J + 1) − DJ J 2 (J + 1)2
Detection by secondary effects 4B 3
Laser-induced fluo: promote molecules to excited state, detect fluo using a PMT, optical filter DJ = Centrifugal distortion constant
ν̃02
ot light trap to reduce scattered light.
(+) Zero bg, best sensitivity
(+) Can obtain position sensitive info, 2D mapping Polyatomic molecule and isotopix substitution
(−) Molecule may have low fluo For spherical rotor: no dipole moment, no pure rotational spectrum
(−) Relative methode: absolute concentration not easily measured 2 P 2 +P 2 +P 2
E = P2I = 1 2I2 3 with P = J(J + 1)ℏ
p
Photoluminescence: Emi results from the difference in energy of the excited e-. Complementary For symmmetric rotor: One moment of inertia I∥ and the others I⊥
to absorption. Spectrum contains peaks related to energy of each excited level.
Photoacoustic: Abs ⇒ excitation ⇒ relaxation ⇒ heating ⇒ thermal expansion ⇒ pressure P12 P 2 + P32
wave ⇒ accoustic detection E= + 2
2I∥ 2I⊥
Resolution
F (J, K) = BJ(J + 1) + (A − B)K 2 K Quantum number
Smallest observable separation between 2 closely spaced spectral bands.
λ ν
Resolving power: R = dλ = dν = dω̃ω̃ Pa = Kℏ , A =
ℏ
and B =
ℏ
R = mN for m diffraction. 4πcI 4πcI
1
Resolution of FT is determined by the max path lenght difference: dω̃ = 2ρmax

Rotational spectroscopy |K| close to its max value, J, most of molecular rotation is around the principal axis.
Moments of inertia K = 0 molecule has no angular momentum. End over end rotation.
mi ri2
P
I= Rotational Raman Spectro
m1 m2 2
Diatomic: I = µr2 = m1 +m2
r
Rotational selection rule: ∆J = 0, ±2
(m1 r−m3 r′ )2
Triatomic: I = m1 r2 + m3 r′2 − m1 +m2 +m3
If molecule gains energy, scattered photo, is red-shifted: Stokes.
∆ω̃ = −4B J + 23


• Linear rotors: 1 moment = 0, I3 = I2 and I1 = 0
If molecule loses
energy, scattered photon is bue-shifted: anti-Stokes.
• Spherical rotors: 3 equal moments, I1 = I2 = I3
∆ω̃ = 4B J + 32
• Symmetric rotors: 2 equal moments, I3 = I2 ̸= I1
• Assymetric rotors: 3 differents moments, I3 ̸= I2 ̸= I1 Vibrational Spectroscopy