Ch1 Spectroscopy 1. More than half of all instrumental methods of analysis involve the absorption or emission of light.

Thus the degree of light absorption and the intensity of light emission are the critical measurements 2. Characterizing Light Particle theory of light Wave theory of light Electromagnetic Wave3. 3. Radiant Energy (Wave theory) Luminance () : : : ds Luminous intensity ( )

Absorption cross section : Number density of absorbers = ln 10 = 2.303 6. Cuvette made of plastic, glass, or fused quartz (for UV

: : 4.Photon Energy

Wavenumber=1/() 5.AbsorptionExcitati

onEmission

5.Beers Law For liquids

For gases

: Transmission (or transmissivity) : Absorption coefficient of the substance : Path length : Molar absorptivity (extinction coefficient) of the absorber : Molar concentration of absorbing species in the material :

the absorption maximum about 30 nm in the same direction. Increased conjugation brings the HOMO and LUMO orbitals closer together. When two double bonds are conjugated, the four -atomic orbitals combine to generate four -molecular orbitals (two are bonding and two are antibonding).In a similar manner, the three design to another and is double bonds of a conjugated polyene create called the resolution. six -molecular orbitals, light) Beers Law Absorption Filters half bonding and half Plot anti-bonding. Wavelength of Limitations of UV-VIS Maximum Spectroscopy Absorbance Sample: The larger the Monochromators works well on liquids and molar absorptivity, solutions solid will scatter the more sensitive the light the method. The Calibrationand reference: greatest analytical Blank reference will be needed( Choice of solvent: An entrance slit, a Every solvent has a dispersing element, and UV-vis absorbance cutoff an exit slit. wavelength which the sensitivity occurs Luminescence solvent itself absorbs all at the wavelength Phosphorescence (): of the light at which the Luminescence resulting Choice of container: absorptivity is a from a jump back to also have a UV-vis maximum. the ground state after absorbance cutoff Ch2UltravioletvisibleSpe routing through other Concentration of solution: ctrometry electronic states (triplet This technique is state,) is complementary called phosphorescence. ( HOMO / LUMO and Bandgap ( HOMO: Highest occupied molecular 4.Photoluminescence(PL) orbital or called probing the electronic Valence band. structure of materialsOne LUMO: Lowest way this excess energy (h) unoccupied molecular can be dissipated by orbital, or called the sample is through the Light Sources Conduction band emission of light, or Visible light( Bandgap: The difference luminescence The UV light of the energies of the excitation wavelength Ultraviolet-Visible HOMO and LUMO should be lower than the light( The smaller the energy, PL wavelength of the Xenon Arc LampA the more easily it will be measured material. excited. Relationship to UV-VIS Conjugation and PL The spectrum on the below illustrates that conjugation of double and triple bonds also shifts the absorption continuous ultraviolet and maximum to longer excitation visible emission wavelengths. spectrum is a graph of contains xenon at a fairly It is clear that each emission intensity high pressure and the additional double bond in versus excitation light is formed via a the conjugated wavelength discharge across a pair of -electron system shifts PL electrodes

BandwidthandResolution The width of the band that is allowed to pass is called the bandwidthThe narrowness of the band that is allowed to pass varies from one

Bandgap determination Recombination emchanisms excited states The simplest photoluminescent processes are resonant radiations, in which a photon of a particular wavelength is absorbed and an equivalent photon is immediately emitted. PL Light emission patterns Absorption and Emission ACQ, TICT and AIE Aggregation-caused quenching (ACQ): fluorescence is weakened with an increase in its solution concentration Aggregation-induced emission (AIE) exactly opposite to the ACQ effect twisted intramolecular charge transfer(TICT) Excitation Wavelength Dependent CH4X-Ray Photoelectron Spectroscopy (XPS) measures the elemental composition, empirical formula, chemical state and electronic state of the elements by irradiating a material with a beam ofX-rays while simultaneously measuring the kinetic energy and number of electrons that escape from the top 1 to 10 nm of the material being analyzed. XPS requires ultra-high vacuum (UHV) conditions (10 -8 Torr). Function and Application XPS detects all elements with an atomic number (Z) of 3 (lithium) and above Detection limits for most of the elements are in the parts per thousand range(ppm) Alias Names of XPS ESCA: Electron spectroscopy for chemical analysis UPS: Ultraviolet photoelectron spectroscopy PES: Photoemission

spectroscopy

momentum : Spin angular momentum Peak Area Ratios 2p 1/2 electrons have a smaller kinetic energy in

Electron Configurations Fundamental Theory of XPS = + + : Photon energy from X-ray source : Kinetic energy of the electron : Binding energy of the sample : Work function of spectrometer Work function: Energies required to remove electrons from the Fermi

comparison to the 2p 3/2 . The integrated intensity of the 2p 1/2signal is half of that of 2p 3/2 due to the difference of the energetic degeneration of both terms ( + ). Peak separation is increased with heavier atoms. X-ray Induced Auger

Electrons Satellite Peak & Shake-up Peak During the emission of a photoelectron one may to vacuum levels binding energy get an additional excitation of a second

large bandgap the intensity of the XPS signal goes back to the level at the leading edge with a smaller binding energy for several eV and then increases. This feature mirrors the bandgap of the material. For metals, electrons may be excitedwith any energy and no gap is observed. background subtraction by Shirley method assumes that the background increases with the binding energy proportionally to the part of the signal immediately before a given energy. For the background subtraction, it must include or correct for X-ray satellites chemically shifted specie Shake-up peaks Plasmon or other losses Quantitative XPS of a peak : Average atomic concentration of element in the surface : Relative sensitivity factors (RSF)

XPS Spectrum XPS spectrum is to measure intensities of photoelectrons vs. Spin Orbital Splitting For p, d and f peaks, two peaks are observed.The separation between the two peaks are named spin orbital splitting, which is attributed to L-S coupling (). L-S coupling Peak notations L-S coupling ( = + ) : Total angular momentum : Orbital angular

electron.The related distribution of the energy to both processes causes a shift of the photoelectron to larger binding energy, which yields a satellite peak. If the second electron is also ejected the satelliteis called a shake-off peak, if it is only excited to a higher electronic level it is called a shake-uppeak.Shake-up satellites are observed for Cu(II)-ions. They have only partially filled d-levels,which may accept an excited electron from anions of an appropriate compound. Effect of Bandgap If the sample is an insulator or a semiconductor with a