1. Spectroscopic and related techniques in surface science for unravelling heterogeneously catalyzed reaction mechanisms
Ludo Juurlink, Ph.D.
Leiden Institute of Chemistry
Leiden University, Leiden, the Netherlands
Office: Gorlaeus Laboratories DE0.01
phone
Course objectives: 
At the this short course students
can explain how surface science attempts to understand heterogeneous catalysis
can outline how common experimental (spectroscopic) techniques reveal information on surfaces, adsorbates, and chemical reactions
Understand why and how (supersonic) molecular beams are useful herein
are informed on some recent examples in the field of gas-surface dynamics

2. Surface Science and Gas-Surface Reaction Dynamics
Schedule
Date
Time
Topics
14-Dec-17
11:00 – 11:50
Introduction: Surface Science for Catalysis
Surface Crystallography
Low Energy Electron Diffraction
Scanning Tunneling Microscopy
12:00 – 12:50
Introduction to spectroscopic techniques
Auger Electron Spectroscopy
X-ray photoelectron spectroscopy
Reflection Absorption InfraRed Spectroscopy
Temperature Programmed Desorption
15-Dec-17
Controlling molecular impact: supersonic molecular beams
Examples of combined use of SMB and Surface Science
Examples from the recent literature on CH4
State-selected dissociation
Mode-selected dissociation
Bond-selected dissociation
Stereodynamical effects

3. Strongly activated dissociation of methane
CH4/Ni(111) and Ni(100)
Lee, Yang, and Ceyer, J. Chem. Phys. 87, 2724 (1987)
Holmblad, Wambach, and Chorkendorff, J. Chem. Phys. 102, 8255 (1995)

4. Some recent state-selected studies for CH4

5. Obtaining state resolution for CH4
Catalytic Surface Science - JuurlinkMarch 20, 2012
March 20, 2012
Obtaining state resolution for CH4
12/2/2018
~35 kJ/mol
~18kJ/mol
~36 kJ/mol
~16 kJ/mol
Juurlink, Killelea and Utz, Surf. Sci. Rep. 84, 69 (2009)

6. Juurlink, Killelea and Utz, Surf. Sci. Rep. 84, 69 (2009)
State selectivity
CH4/Ni(100) and Ni(111)
CH4 dissociation is greatly enhanced by excitation of a stretch vibration.
A quantum of antisymmetric stretch enhances reactivity approx as much as the same amount of kinetic energy
The second quantum of antisymmetric stretch vibration helps as much as the first.
The symmetric stretch is much more efficient in progressing along the reaction path than the antisymmetric stretch.
v = 2 (3)
v = 1 (1)
v = 1 (3)
v = 0
Juurlink, Killelea and Utz, Surf. Sci. Rep. 84, 69 (2009)

7. State selectivity CH4/Ni(100) and Ni(111)
Again, stretch vibrations help; here v=1 (3) is more effective than Ekin!
The 2nd quantum of antisymmetric stretch vibration does not help as much as the first.
The antisymmetric bending vibration helps considerably less than the antisymmetric stretch on a “per energy basis” in v=3.
v = 2 (3)
v = 1 (3)
v = 3 (4)
State selectivity
It matters where you put the energy
v = 0
Energy efficiency
The more activated the system the more crucial how energy is supplied.
Juurlink, Killelea and Utz, Surf. Sci. Rep. 84, 69 (2009)

8. Mode selectivity CD2H2/Pt(111) |20> |11> |00> 5879.8 cm-1
70.4 kJ/mol
cm-1
71.8 kJ/mol
Beck et al, Science 302, 98 (2003)

9. It matters where you put the energy!
Bond selectivity
CD3H/Ni(111)
C-D cleavage
C-H cleavage
CD3
CD2H
CD4
CD3H
Bond-selectivity.
It matters where you put the energy!
Killelea, Campbell, Shuman, and Utz, Science 319, 790 (2008)

10. Stereodynamical effects
CH4/Ni(100)
The initial state (0) or (1) indicates quantum number N, which is
body rotation of the molecule. For the initial state N=J. For the upper state N can not have changed. 2
v=1 1
P(1)
R(0) 2 1
v=0
Yoder, Regis, and Beck, Science 329, 553 (2010)

11. Surface Science and Gas-Surface Reaction Dynamics
Schedule
Date
Time
Topics
14-Dec-17
11:00 – 11:50
Introduction: Surface Science for Catalysis
Surface Crystallography
Low Energy Electron Diffraction
Scanning Tunneling Microscopy
12:00 – 12:50
Introduction to spectroscopic techniques
Auger Electron Spectroscopy
X-ray photoelectron spectroscopy
Reflection Absorption InfraRed Spectroscopy
Temperature Programmed Desorption
15-Dec-17
Controlling molecular impact: supersonic molecular beams
Examples of combined use of SMB and Surface Science
Examples from the recent literature on CH4
State-selected dissociation
Mode-selected dissociation
Bond-selected dissociation
Stereodynamical effects