UV-Vis spectroscopy

Dr. Davide Ferri

Paul Scherrer Institut
056 310 27 81
davide.ferri@psi.ch
The electromagnetic spectrum

VISIBLE ULTRAVIOLET

1015-1016 Hz 1016-1017 Hz

200

source: Andor.com
 UV-vis spectroscopy

Use of ultraviolet and visible radiation

Electron excitation to excited electronic level (electronic transitions)
Identifies functional groups (-(C=C)n-, -C=O, -C=N, etc.)
Access to molecular structure and oxidation state

pros IR
economic Raman

non-invasive (fiber optics!) NMR

versatile (e.g. solid, liquid, gas) XAFS

extremely sensitive (concentration) UV-Vis

fast acquisition (but S/N!) EPR

0 200 400 600 800 1000 1200

Number of publications
cons
no atomic resolution
broad signals (spectral resolution, multiple overlapping components)
 Electronic transitions
hν

Organic molecule Organic molecule

anti-bonding anti-bonding
σ*
empty
π*
lone pairs e e n e e
occupied e π e
bonding bonding
e σ e

n→π* n→σ* π→π* σ→σ* n→π* n→σ* π→π* σ→σ*

E= hν λ= c/ν

high e- jump → high E

high E → high ν high ν → low λ
 Electronic transitions

anti-bonding
σ*

π*
e e n
e π
bonding
e σ
n→π* n→σ* π→π* σ→σ*

σ→σ* n→π* Condition to absorb light

high E, low λ (<200 nm) 200-700 nm, weak (200-800 nm):

n→σ* π and/or n orbitals

150-250 nm, weak π→π*
200-700 nm, intense CHROMOPHORE
 The UV spectrum
1.0 λmax
217 nm

σ* 0.8

π*

absorbance
0.6
n
0.4
e π
0.2
σ
0.0 no visible light absorption
π→π*
200 220 240 260 280 300

wavelength (nm)
signal envelope

vibrational
E*
energy

electronic levels
How many signals do you
expect from CH3-CH=O?
rotational
electronic levels
E0
 The UV spectrum
Conjugation effect
delocalisation λmax λ ν E

171

217

258

C2H4 C4H6 C6H8

π*

e
e
e π
 The UV spectrum
Conjugation effect: β-carotene
white light

absorbance

300 360 420 480 540

wavelength (nm)
 The UV spectrum
Complementary colours

650 - 780 380 - 435

580 - 595 435 - 480

500 - 560 480 - 490

If a colour is absorbed by white light, what the eye detects

by mixing all other wavelengths is its complementary
colour
 Inorganic compounds
UV-vis spectra of transition metal complexes originate from

Electronic d-d transitions

dσ

eg
degenerate
d-orbitals

+ ligand ∆

TM

t2g
TM
dπ

…
 Inorganic compounds
dx2-y2
Crystal field theory (CFT) - electrostatic model
same electronic structure of central ion as in isolated ion
perturbation only by negative charges of ligand
dx2-y2, dz2
dx2-y2

dxy, dxz, dyz

dz2
∆
atom in
spherical field
∆ ∆

dx2-y2, dz2 dxy

dxy
gaseous atom
dxy, dxz, dyz

dyz, dxz
∆ = crystal field splitting dz2

tetrahedric octahedric tetragonal square planar

field field field field
 Inorganic compounds
d-d transitions: Cu(H2O)62+
eg
degenerate
d-orbitals

∆ light
+ 6H2O

Cu2+
t2g

Cu(H2O)62+

Yellow light is absorbed and the Cu2+ solution is coloured in blue (ca. 800 nm)
The greater ∆, the greater the E needed to promote the e-, and the shorter λ
∆ depends on the nature of ligand, ∆NH3 > ∆H2O
 Inorganic compounds
TM(H2O)6n+

elec. config. TM
gas complex Cu2+ Fe2+
3d1 t2g1 Ti(H2O)63+ Ni2+ Co2+
3d2 t2g1 Ti(H2O)63+
3d3 t2g3 absorbance
Cr(H2O)63+
3d4 t2g3eg1 Cr(H2O)62+ Cr3+
3d5 t2g3eg2 Mn(H2O)62+
Ti3+ V4+
3d6
3d7
3d8
3d9 t2g6eg3 Cu(H2O)62+

400 500 600 700 800 900 1000

wavelengths (nm)

d-d transitions: εmax = 1 - 100 Lmol-1cm-1, weak

 Inorganic compounds
d-d transitions: factors governing magnitude of ∆

Oxidation state of metal ion

∆ increases with increasing ionic charge on metal ion

Nature of metal ion

∆ increases in the order 3d < 4d < 5d

Number and geometry of ligands

∆ for tetrahedral complexes is larger than for
octahedral ones

Nature of ligands
spectrochemical series

I- < Br- < S2- < SCN- < Cl- < NO3- < N3- < F- < OH- <
C2O42- < H2O < NCS- < CH3CN < py < NH3 < en <
bipy < phen < NO2- < PPh3 < CN- < CO
 Inorganic compounds
UV-vis spectra of transition metal complexes originate from

Electronic d-d transitions

eg
degenerate
d-orbitals

+ ligand ∆

TM

t2g
TM

Charge transfer
 Inorganic compounds
Charge transfer complex

no selection rules → intense colours (ε=50‘000 Lmol-1cm-1,

strong)

Association of 2 or more molecules in which a fraction of

electronic charge is transferred between the molecular
entities. The resulting electrostatic attraction provides a
stabilizing force for the molecular complex

Electron donor: source molecule

Electron acceptor: receiving species

CT much weaker than covalent forces

Ligand field theory (LFT), based on MO

Metal-to-ligand transfer (MLCT)
Ligand-to-metal transfer (LMCT)
 Inorganic compounds
Ligand field theory (LFT)
involves AO of metal and ligand, therefore MO
what CFT indicates as possible electronic transitions (t2g→eg)
are now: πd→σdz2* or πd→ σdx2-y2*
πpx*, πpy*, πpz*

σp *
4p
σs *

σd *
4s eg
∆
t2g
πdxy, πdxz, πdxy 2s
3d
σd

AOTM AOL
σp
∆ = crystal field splitting
σs

MO(TML6n+)
 Inorganic compounds
Ligand field theory (LFT)

LMCT
ligand with high energy lone pair
or, metal with low lying empty orbitals
high oxidation state (laso d0) 4σ
M-L strengthened 2π∗ 2π∗
O
1π 1π
3σ
C
MLCT
2π∗ 5σ 2π∗
ligands with low lying π* orbitals (CO, CN-, SCN-)
low oxidation state (high energy d orbitals)
Metal
M-L strengthened, π bond of L weakened
back donation!!!

CO adsorption on
precious metals
 Band gap
■ Analysis of semiconductors
Photocatalysis

A+
TiO2, 3.2 eV
reduction
energy A+ 1e- A+

CB e- A

band
gap

VB +
B
oxidation
B+ h+ B-
B-
 Band gap
DIRECT INDIRECT
energy energy

CB CB

phonon

VB VB

k k

How to measure
inflection point
energy at exp. increase
intercept energy axis
 Instrumentation
Dispersive instruments

Measurement geometry:
- transmission
- diffuse reflectance

double beam spectrometer

single beam spectrometer

 In situ instrumentation
Diffuse reflectance (DRUV) Fiber optics

to detector

gas outlet - time resolution (CCD camera)

[spectra colleted at once]
- coupling to reactors
- 20% of light is collected
- no NIR (no optical fiber > 1100 nm)
- gas flows, pressure, vacuum
- long term reproducibility (single beam)
- Limited high temperature (ca. 600°C)
- long meas. time
- spectral collection (λ after λ)
→ different parts of spectrum do not represent same reaction time!!!

Weckhuysen, Chem. Commun. (2002) 97

 In situ instrumentation
Integration sphere

White coated integration sphere

(MgO, BaSO4, Spectralon®)

integration
- > 95% light is collected
sphere
- high reflectivity
- wide range of λ

- only homemade cells

for example, for cat. synthesis

Weckhuysen, Chem. Commun. (2002) 97

 Examples
Determination of oxidation state: 0.1 wt% Crn+/Al2O3

Cr6+ (250, 370 nm)

reduction in CO atmosphere
Cr3+/Cr2+

Weckhuysen et al., Catal. Today 49 (1999) 441

 Examples
Determination of oxidation state: 0.1 wt% Crn+/Al2O3
calibration

Cr3+ distribution of Crn+

100

Cr6+
Cr6+
% 50
Cr5+
Cr3+
Cr2+

deconvolution
0
A B C D E F
A: calc. 550°C
B: red. 200°C
C: red. 300°C
D: red. 400°C
E: red. 600°C
F: re-calc. 550°C

Weckhuysen et al., Catal. Today 49 (1999) 441

 Examples
UV-vis probe in a pilot-scale reactor: propane dehydrogenation

GC

10 vol% C3H8, 90 vol% N2, 5000 ml/min

20 wt% Cr3+/6+Ox/Al2O3

Weckhuysen et al., Chem. Commun. 49 (2013) 1518

 Examples
UV-vis probe in a pilot-scale reactor
bottom UV-vis probe average intensity 600-700 nm
dehydrogenation
top UV-vis
probe
bottom UV-vis
probe

regeneration bottom UV-vis

probe

top UV-vis
probe

Coke formation fast on top section of reactor

Coke is combusted fast in top section of reactor
Weckhuysen et al., Chem. Commun. 49 (2013) 1518