1. Vibrational
1.1. IR
1.1.1. Degrees of freedom (normal modes)
1.1.1.1. Linear
1.1.1.1.1. 3N-5 as only 2 rotational
1.1.1.2. non linear
1.1.1.2.1. 3N-6
1.2. Raman
1.2.1. Exclusion rule
1.3. Vibrations of molecules
1.3.1. Symmetrical stretching
1.3.2. Asymmetrical stretching
1.3.3. Scissoring (Bending)
1.3.4. Rocking
1.3.5. Wagging
1.3.6. Twisting
1.4. Harmonic oscillator
1.4.1. V(x)=0.5kx^2
1.4.2. Ev=(v+0.5)hv
1.4.3. Energy Level
1.4.3.1. equally spaced: hv
1.4.3.2. v=1/2π(k/µ)^1/2
1.4.4. limitations
1.4.4.1. no dissociation of molecule
1.5. Anharmonicity
1.5.1. Energy Level
1.5.1.1. Ev=(v+0.5)hv-(v+0.5)^2 hv xe (anharmonicity constant)
1.5.2. Intensity
1.5.2.1. overtone
1.5.2.1.1. (+T) --> (-Intensity)
1.5.2.2. hotband
1.5.2.2.1. weaker than fundamental
1.5.2.2.2. (+T) --> (+hot band) but (-fundamental)
1.5.3. overtones
1.5.3.1. first overtone: v=0 to v=2
1.5.3.2. second overtone: v=0 to v=3
1.5.4. hot band
1.5.4.1. first hot band: v=1 to v=2
1.5.4.2. second hot band: v=2 to v=3
2. Vibro-rotational
2.1. Raman
2.1.1. OQS branch
2.1.1.1. O: J=-2; Q: J=0 always allowed; S: J=+2
2.2. IR
2.2.1. Energy Level
2.2.1.1. Evj=(v+0.5)hv+hBJ(J+1)
2.2.1.1.1. vR=v+2B(J+1)
2.2.1.1.2. vP=v-2BJ
2.2.2. PQR branch
2.2.2.1. P: J=-1; Q: J=0; R: J=+1
2.2.2.2. Q found in polyatomic molecules, except NO
2.3. real spectrum
2.3.1. R converge; P diverge
2.3.2. anharmonicity
2.3.3. centrifugal distortion
2.3.3.1. Bj=Bo-DJ(J+1)
3. Photoelectron
3.1. Ionization Energy
3.1.1. Ekin=hv-Ii
3.2. XPS
3.2.1. Photoelectron spectrum
3.2.1.1. electron from σ bond
3.2.1.1.1. fine structure: vibrational excitation
3.2.1.2. electron from lp
3.2.1.2.1. lack of vibrational structure
3.2.1.2.2. slight change of equilibrium bond length
3.3. Peak broadening
3.3.1. Instrumental
3.3.2. Physical
3.3.2.1. Lifetime
3.3.2.1.1. Collisional deactivation
3.3.2.1.2. Spontaneous emission
3.3.2.2. Doppler
3.3.2.2.1. To minimize: low pressure
3.3.2.2.2. approaching: λ compressed; receding: λ expanded
3.3.2.2.3. Temp dependent
4. Rotational
4.1. Raman
4.1.1. Polarizability
4.1.1.1. isotropic
4.1.1.2. anisotropic
4.1.2. Raman Shift
4.1.2.1. Energy Level
4.1.2.1.1. v=2B(2J+3)
4.1.2.1.2. First separation: 6B, other: 4B
4.1.3. Intensity
4.1.3.1. anti-stokes lower
4.1.3.1.1. lower no. of molecules present in lower energy state before irradiation
4.2. Microwave
4.2.1. Intensity
4.2.1.1. Transition Probability
4.2.1.2. Population Pj
4.2.1.2.1. Jmax=[(kT/2hB)^0.5]-0.5
4.2.2. Energy Level
4.2.2.1. Energy Level (Linear and spherical)
4.2.2.1.1. B=ħ/4πI
4.2.2.1.2. Ej=hBJ(J+1)
4.2.2.1.3. vj=2B(J+1)
4.2.2.1.4. equally spaced = 2B
4.2.2.2. Energy Level (Symmetric)
4.2.2.2.1. Ej,k=hBJ(J+1)+h(A-B)K^2
4.3. Rigid Rotor
4.3.1. Linear
4.3.1.1. diatomic
4.3.1.1.1. I=μR^2
4.3.1.2. triatomic
4.3.1.2.1. I=2mr^2
4.3.2. Symmetric
4.3.3. Asymmetric
4.3.4. Spherical
4.4. Non- Rigid Rotor
4.4.1. Centrifugal distortion
4.4.1.1. Increases I and decreases B
4.4.1.2. Ej=hBJ(J+1)-hDJ^2 (J+1)^2
4.4.1.3. D ̃=(4B ̃^3)/v ̃^2
4.5. Orientation in space: Mj (Linear)
4.5.1. 2J+1 orientations with respect to an external axis
4.5.1.1. 2J+1 degenerate states at J level
4.5.1.1.1. Stark effect: measure permanent dipole moment
5. UV-Vis
5.1. types of electronic transitions
5.1.1. organic
5.1.2. Inorganic
5.1.2.1. transition between d orbitals
5.2. Vibrational fine structure
5.2.1. Resolving fine structure
5.2.1.1. state: gas phase
5.2.1.2. Temp: low T
5.2.1.3. Solvent: apolar
5.2.2. Franck-Condon Principle
5.2.2.1. intensity
5.2.2.1.1. vibration state vertically above; Largest overlap between vibrational wavefunctions
5.2.3. Number of bands
5.2.3.1. relative position of the potential E curve
5.2.3.1.1. Horizontal Displacement and its direction
5.2.3.2. steepness of the curve
5.3. Rotational structure
5.3.1. bond length
5.3.1.1. greater than ground state: R lines converge
5.3.1.2. shorter than ground state: P lines converge
5.4. Jablonski diagram
5.4.1. singlet
5.4.1.1. Fluorescence
5.4.1.1.1. S to S*
5.4.2. triplet
5.4.2.1. Phosphorescence
5.4.2.1.1. S to T (intersystem crossing)