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Spectroscopy in
Inorganic Chemistry
UV-VIS
Part 2
08/2018
Electronic
Transitions
2
Spectroscopic method uv part 2  organic mol and np
METAL NANOPARTICLES
SPR (Surface Plasmon Resonance)
https://www.sigmaaldrich.com/technical-documents/articles/materials-
science/nanomaterials/silver-nanoparticles.html
The strong interaction of the silver nanoparticles
with light occurs because the conduction
electrons on the metal surface undergo a
collective oscillation when excited by light at
specific wavelengths
Color (absorption maximum) corresponds to particle size.
Example: AgNP
Spectroscopic method uv part 2  organic mol and np
Applications of AgNP
Diagnostic Applications: Silver nanoparticles are used in biosensors and
numerous assays where the silver nanoparticle materials can be used as
biological tags for quantitative detection.
Antibacterial Applications: Silver nanoparticles are incorporated in
apparel, footwear, paints, wound dressings, appliances, cosmetics, and
plastics for their antibacterial properties.
Conductive Applications: Silver nanoparticles are used in conductive inks
and integrated into composites to enhance thermal and electrical
conductivity.
Optical Applications: Silver nanoparticles are used to efficiently harvest
light and for enhanced optical spectroscopies including metal-enhanced
fluorescence (MEF) and surface-enhanced Raman scattering (SERS).
Analyze these 4 samples of AgNP
Influence of stabilizer
Reduction of AgNO3 by Na-citrate +/- PVP
No PVA + PVA
https://file.scirp.org/pdf/JMP_2015072215535041.pdf
Number of atoms in one NP
d = diameter of NP
 = density of the metal
M = molar mass of the metal
http://scholarcommons.usf.edu/ujmm/vol7/iss1/2/
Conc. of NP in “solution”
Lambert-Beer applied:
cf curcumin in DMSO: 5.54 * 104 M-1cm-1
Gold NP:  max = 517 nm =>  = 1.1 * 10 7 (or 8 !?!)
Estimation of particle size for AuNP
d = diameter of NP
0 = 512 nm
L1 = 6.53
L2 = 0.0216
https://pubs.acs.org/doi/pdf/10.1021/ac0702084
{for d > 25 nm)
Alternative method using Absorption values:
Experimental parameters:
B1 = 3.00
B2 = 2.20
https://pubs.acs.org/doi/pdf/10.1021/ac0702084
ORGANIC MOLECULES (LIGANDS)
Normally only 2 types of electronic transitions:
Which transitions are possible for Formaldehyde ?
Electronic transition selection rules
(1) S = 0 (spin selection)
(2) l= ±1 (orbital selection / Laporte rule)
There must be a change in orbital symmetry
(3) the direct product i,el * j,el transforms like
x, y or z
http://www.southampton.ac.uk/~pileio/peppesoton/Teaching/Entries/2009
/3/10_Symmetry_and_Molecular_Spectroscopy_-
_PG510_files/Lecture_6.pdf
19
Example Butadiene
Ground state:
2 el in Au and 2 el in Bg => product: Au x Au x Bg x Bg = Ag
Excited state:
Au x Bg x Au x Au = Bu x Ag = Bu
Transition Ag -> Bu: product is Bu -> has x/y component
=> transition allowed 20
Summary of usual electron transitions
http://www.chemguide.co.uk/analysis/uvvisible/theory.html
Conjugated  systems
More conjugated double
bonds cause
1. Redshift
2. Higher peaks
Example: Curcumin Complexes
Anti-Cancer activity
Ox.no. change on metal
Under certain situations, Cu(II) can be reduced to Cu(I), thereby
forming a radical as intermediate.
This could serve as “radical scavenger”
Curcumin in CH3CN
plus Cu(II)
Curcumin in CH3OH
plus Cu(II)
Curcumin in CH3CN
SEMICONDUCTORS
Spectroscopic method uv part 2  organic mol and np
FLUORESCENCE (LUMINISCENCE)
SPECTROSCOPY
Triplet
States
Flouresence emission always
occurs from the LOWEST
vibrational excited state
BECAUSE:
the relaxation process is fast !
http://micro.magnet.fsu.edu/primer/techniques/fluorescence/fluorescenceintro.html
Absorption
Emission (A)
Det
Det
Emission (B)
Det
Det
Excitation
We measure the excitation spectrum in order to find out the
best wavelength, which we should use for the emission
spectrum – example:
Excitation vs Emission Spectrum
Advantages
• More sensitive when compared to other
absorption techniques. Concentrations as low
as μg/ml or ng/ml can be determined.
(One molecule can emit light many times, but in
absorption only one time)
• Precision up to 1% can be achieved easily
• As both excitation & emission wave lengths
are characteristic it is more specific than
absorption methods.
Inorganic Analysis
• Is in competition to AAS for metal cations
• Especially useful for uranium salts
• And for certain anions like (a) cyanide:
Absorption at 400 nm,
emission at 480 nm
0.2 – 50 ug/L
(b) Phosphate:
An ion association complex between molybdophosphate and rhodamine B
provides the basis for an assay for phosphorous at 0.04 to 0.6 µg. The
fluorescence is measured at 575 nm with an excitation at 350 nm, after first
extracting excess of the rhodamine with chloroform.
(c) Flouride
The End of Part 1

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Spectroscopic method uv part 2 organic mol and np

  • 5. SPR (Surface Plasmon Resonance) https://www.sigmaaldrich.com/technical-documents/articles/materials- science/nanomaterials/silver-nanoparticles.html The strong interaction of the silver nanoparticles with light occurs because the conduction electrons on the metal surface undergo a collective oscillation when excited by light at specific wavelengths
  • 6. Color (absorption maximum) corresponds to particle size. Example: AgNP
  • 8. Applications of AgNP Diagnostic Applications: Silver nanoparticles are used in biosensors and numerous assays where the silver nanoparticle materials can be used as biological tags for quantitative detection. Antibacterial Applications: Silver nanoparticles are incorporated in apparel, footwear, paints, wound dressings, appliances, cosmetics, and plastics for their antibacterial properties. Conductive Applications: Silver nanoparticles are used in conductive inks and integrated into composites to enhance thermal and electrical conductivity. Optical Applications: Silver nanoparticles are used to efficiently harvest light and for enhanced optical spectroscopies including metal-enhanced fluorescence (MEF) and surface-enhanced Raman scattering (SERS).
  • 9. Analyze these 4 samples of AgNP
  • 10. Influence of stabilizer Reduction of AgNO3 by Na-citrate +/- PVP No PVA + PVA https://file.scirp.org/pdf/JMP_2015072215535041.pdf
  • 11. Number of atoms in one NP d = diameter of NP  = density of the metal M = molar mass of the metal http://scholarcommons.usf.edu/ujmm/vol7/iss1/2/
  • 12. Conc. of NP in “solution” Lambert-Beer applied: cf curcumin in DMSO: 5.54 * 104 M-1cm-1
  • 13. Gold NP:  max = 517 nm =>  = 1.1 * 10 7 (or 8 !?!)
  • 14. Estimation of particle size for AuNP d = diameter of NP 0 = 512 nm L1 = 6.53 L2 = 0.0216 https://pubs.acs.org/doi/pdf/10.1021/ac0702084 {for d > 25 nm)
  • 15. Alternative method using Absorption values: Experimental parameters: B1 = 3.00 B2 = 2.20 https://pubs.acs.org/doi/pdf/10.1021/ac0702084
  • 17. Normally only 2 types of electronic transitions:
  • 18. Which transitions are possible for Formaldehyde ?
  • 19. Electronic transition selection rules (1) S = 0 (spin selection) (2) l= ±1 (orbital selection / Laporte rule) There must be a change in orbital symmetry (3) the direct product i,el * j,el transforms like x, y or z http://www.southampton.ac.uk/~pileio/peppesoton/Teaching/Entries/2009 /3/10_Symmetry_and_Molecular_Spectroscopy_- _PG510_files/Lecture_6.pdf 19
  • 20. Example Butadiene Ground state: 2 el in Au and 2 el in Bg => product: Au x Au x Bg x Bg = Ag Excited state: Au x Bg x Au x Au = Bu x Ag = Bu Transition Ag -> Bu: product is Bu -> has x/y component => transition allowed 20
  • 21. Summary of usual electron transitions http://www.chemguide.co.uk/analysis/uvvisible/theory.html
  • 23. More conjugated double bonds cause 1. Redshift 2. Higher peaks
  • 26. Ox.no. change on metal Under certain situations, Cu(II) can be reduced to Cu(I), thereby forming a radical as intermediate. This could serve as “radical scavenger”
  • 27. Curcumin in CH3CN plus Cu(II) Curcumin in CH3OH plus Cu(II) Curcumin in CH3CN
  • 32. Flouresence emission always occurs from the LOWEST vibrational excited state BECAUSE: the relaxation process is fast !
  • 35. We measure the excitation spectrum in order to find out the best wavelength, which we should use for the emission spectrum – example:
  • 37. Advantages • More sensitive when compared to other absorption techniques. Concentrations as low as μg/ml or ng/ml can be determined. (One molecule can emit light many times, but in absorption only one time) • Precision up to 1% can be achieved easily • As both excitation & emission wave lengths are characteristic it is more specific than absorption methods.
  • 38. Inorganic Analysis • Is in competition to AAS for metal cations • Especially useful for uranium salts • And for certain anions like (a) cyanide: Absorption at 400 nm, emission at 480 nm 0.2 – 50 ug/L (b) Phosphate: An ion association complex between molybdophosphate and rhodamine B provides the basis for an assay for phosphorous at 0.04 to 0.6 µg. The fluorescence is measured at 575 nm with an excitation at 350 nm, after first extracting excess of the rhodamine with chloroform. (c) Flouride
  • 39. The End of Part 1