Modern Methods in Spectroscopy

Lecture 11

June 28, 2022

Q1-3
Fourier-Transform Spectroscopy: Use of a Michelson Interferometer
Radiation Sources

Globar (IR)
Lamps in the VIS, UV (Hg lamp, Xe lamp, …D2 lamp)

Synchrotron Radiation
Beamsplitters and Detectors for FT-IR Spectroscopy

IR-detection
MCT Detector

Semiconductors
With narrow band gap
Detectors for FT-IR Spectroscopy
Interferograms and Molecular Spectra

Intensity
Relative Coordinate of movable mirror

Absorption

Wavenumber [cm-1]
Exercise

?
FTIR-Spectrum of CO
 Classical Absorption Setup for Studying OClO

A. Wahner et al., JPC, 1987

 Temperature Dependent
UV-Absorption of OClO

A. Wahner et al., JPC, 1987

 Fourier-Transform Spectrometer for High-Resolution Studies on OClO

E.C. Richard et al, JCP 1987

 High-Resolution UV Absorption of Thermal and Jet-Cooled OClO

E.C. Richard et al, JCP 1987

 High-Resolution UV Absorption of OClO

Rotational resolution and band head structure

E.C. Richard et al, JCP 1987

 VUV-Absorption Cross Section of OClO

J. Phys. Chem 97, 837 (1993)

VUV-FT Spectroscopy
 VUV-FT-Spectrum of O2

FT (Super-ACO, SU5)

FT (Soleil, Desirs) Interferences due to MgF2 window

 Multiphoton-Absorption

Jet-cooling for simplifying molecular spectra

B AD UV
C CA
C E B BB
R2PI A
B A A
B C D C E B*
B B*C B*
A A
Ion C B*

Boltzmann distribution
of the vibrational
population prior to
expansion Collisional
cooling
S1 to zero-point
vibrational
level

S0

T. Zwier (Purdue)
 UV-chromophore

Jet-cooled UV spectrum
Intensity (arbitrary intensity)

34600 34800 35000 35200 -1 35400 35600

Wavenumbers (cm )

T. Zwier (Purdue)
 Various Excitation Schemes Solvation shifts in excited
S1-state probed via ionization and
Requirements: mass spectrometry
Jet-cooling and narrow bandwidth and
intense laser pulses
FBZ: fluorobenzene

One Color
Two Color
Resonant-Two
Resonant-Two
Photon
Photon
Ionization
Ionization

B. Brutschy Chem. Rev. 1992

 Chemical Reactions in Clusters Probed by R2PI

Anisol is the reaction product

from fluorobenzene + methanol

B. Brutschy Chem. Rev. 1992

 Combinations of IR-Radiation with Multiphoton Ionization

Resonant 2-
photon ionization -> depletion of R2PI-
signal due to IR-absorption
-> depletion of R2PI- of the cation
signal due to IR-absorption
of the neutral
B. Brutschy Chem. Rev. 2000
 Combinations of IR-Radiation with Multiphoton Ionization

Ionization detected photoinduced Rydberg ionization

stimulated Raman spectroscopy

B. Brutschy Chem. Rev. 2000

 IR-Spectra of van der Waals Clusters Derived From
Multiphoton Ionization (probed by Mass Sepctrometry)

B. Brutschy Chem. Rev. 2000

 Excited States of OClO

E.C. Richard et al, JCP 1987

 Multiphoton Ionization of OClO

OClO+ cannot be observed using nanosecond

laser multiphoton ionization due to ultrafast
predissociation into ClO+O

J. Phys. Chem 94, 2990 (1990)

 Multiphoton Ionization of OClO

Formation of Cl+:
Evidence for isomerization of
OClO in ClOO yielding
Cl+O2

J. Phys. Chem 94, 2990 (1990)

Femtosecond Multiphoton Ionization of OClO
 Femtosecond Multiphoton Ionization of OClO

OClO+ can be observed using femtosecond

laser multiphoton ionization due to ultrafast
Ionization that is faster than predissociation
into ClO+O

H. Baumert et al., J. Chem. Phys. 99, 4630 (1993)

Fluorescence and Phosphorescence

A: absorption
F: fluorescence
IC: internal conversion
ISC: intersystem crossing
P: phosphorenscence
S: singulett state
T: triplett state

Jablonski Diagram
Fluorescence Spectrometers
Compact Optical
Spectrometer
Spectral Distributions of Absorption, Fluorescence, and Phosphorescence
 Stokes Shift

W. Schmidt: Optical Spectroscopy…, VCH (2005)

 Stokes Shift: 45 nm

W. Schmidt: Optical Spectroscopy…, VCH (2005)

 Anti-Stokes Shifts

Upconversion
Modes of Fluorescence Measurements

1. Emission scan at fixed

excitation wavelength
2. Excitation scan at fixed
emission wavelength
Time-Resolved Fluorescence of Antracene

Dynamical information
Fluorescence Polarization
 Simple Example: Argon

Fluorescence Excitation Spectra

following Ar 2p-excitation

R. Flesch et al., Phys. Rev. A, 61, 062504 (2000)

 Dispersed Fluorescence Spectra
following Ar 2p-excitation

ba
c

reference

R. Flesch et al., Phys. Rev. A, 61, 062504 (2000)

 Time-Resolved Fluorescence Spectra
following Ar 2p-excitation

R. Flesch et al., Phys. Rev. A, 61, 062504 (2000)

 Interpretation of
Fluorescence Cascades

R. Flesch et al., Phys. Rev. A, 61, 062504 (2000)

 S 2p Excitation of H2S

J. Chem. Phys. 125, 314206 (2006).

 S 2p Excitation of H2S

Mostly emission of Balmer radiation of excited H (H*)

H2S + h -> H* + SH+
J. Chem. Phys. 125, 314206 (2006).
 S 2p Excitation of H2S

Formation of vibrationally
excited SH+

J. Chem. Phys. 125, 314206 (2006).

 S 2p Excitation of H2S

Formation of rotationally
excited SH+ (T900 K)

J. Chem. Phys. 125, 314206 (2006).

 Laser-induced fluorescence

Demtröder
 Fluorescence Excitation Spectra

Structural information
from rotationally resolved
excited state spectra

Hollas
Variation of excitation energy leads to changes
in internal energy distribution, as probed by fluorescence
 X-Ray Fluorescence Yields

Photoelectron
Auger Electron

Vacuum level

Valence
shell

Fluorescence Yield
h
X-ray Fluorescence

Core level

High Z Elements emit

X-Ray Fluorescence

J. Stöhr, NEXAFS Spectroscopy

 Ulbricht Bowl: Determination of the fluorescence quantum yield

[Link]
 Detection Efficiency of Fluorescence

Collection efficiency: 15% of 4

Opening angle

Solid angle