measuring and modeling absolute data for electron-induced processes
Post on 13-Jan-2016
25 Views
Preview:
DESCRIPTION
TRANSCRIPT
1
Measuring and modeling absolute data for electron-induced processes
Michael Allan
Department of Chemistry
University of Fribourg, Switzerland
Chemistry and Spectroscopy with Free Electrons
A personal retrospective
2
1. A very personal retrospective
2. H2 : a short or long-lived resonance?
3. The peculiar story of threshold peaks : HF, HCl, HBr
4. CO2 : threshold peaks are commonplace
5. H-C≡C-H : the necessity of many dimensions
6. HCOOH : the hybrid case
7. Higher energy : CH3OH, C4H9-O-C4H9 etc.
8. Exotic molecules: Pt(PF3)4
9. Many excellent laboratories
10. Where do we find electron collisions ?
11. Conclusions
Contents
3
gloooooooow in the dark
Electron Tubes
magic eye
Pardubice
4
Basel
M. Allan and J. P. Maier 1976
Energy of emitted photon
Energy of incident electron
5
Yale
M. J. W. Boness and G. J. Schulz 1976 A. Stamatovic and G. J. Schulz 1970
6
short – lived radical anions = resonances
backgroundscattering
resonantscattering
coherent
superposition
= 72°
7
Feshbach (g)13s2
valence core-excited (g)1(u)2
Resonances:
shape (g)2(u)1
DEA and VE in H2
“* shape resonance”
Ethreshold
H-/H2
D-/D2
> 200
E(eV)
8
Frustration over instruments
M. J. W. Boness and G. J. Schulz 1973
• Background
• Low energy not accessible
• Only narrow energy range
• Spectrum distorted by instrument’s response function
• Only relative units
• Limited angular range
• ...
9
Fribourg
• Very low background
• Low energy OK
• Wide energy range
• but
• Only relative units
• scattering angle only 0° and 180°
• no elastic scattering
1981 1989
10
Magnetic Angle Changer(Frank H. Read)
Magnetic Angle Changer
see also Andrew J. Murray, Wednesday lecture
11
Juraj Fedor, Olivier May, Dušan Kubala, Fribourg 2008
Time-of-Flight mass spectrometer
for absolute DEA cross section
12
13
14shape resonances
core excited Feshbach resonance
full-range spectrum in N2
15
H2 : a short or long-lived resonance?
16
E(eV)
H2 : a short or long-lived resonance?
1985
calculations:Čížek, Horáček, Domcke
17
looking at large R (high final v) permits time resolution
1993
18
H2 lifetime : going to the extreme
D2 : = 2 ms
Experiment : Golser et al., 2005 (Wienna)
19
Vibrational excitation in HF – naive expectation
* - resonance
Threshold phenomena
20
• threshold peaks
• Vibrational Feshbach Resonances
• dipole – bound resonances
* shape resonance
valence
dipole bound
Čížek, Horáček, Allan, Fabrikant, Domcke 2003
= D
Threshold phenomena
Original discovery: G. Knoth, M. Gote, M. Rädle, K. Jung and H. Ehrhardt, PRL 1989
21
Čížek, Horáček, Allan, Fabrikant, Domcke, J. Phys. B (2003)
HF – theory and experiment
review: Hotop, Ruf, Allan, Fabrikant, Adv. At. Mol. Opt. Phys. 49 (2003) pp 85-216.
22
structures everywhere
23
NO – vibrational excitationboomerang oscillations strongly influenced by existence of
quasi-bound vibrational state of NO
Allan, J. Phys. B (2005)
K. Houfek, M. Čížek, J. Horáček, Chem. Phys. (2008)
24
Chemistry:
Dissociative electron attachment to
diatomic hydrides
e + HBr H + Br
25
Interchannel Coupling in Dissociative Atachment
COMPARISON OF ABSOLUTE CROSS SECTIONS !
blue: nonlocal resonance theoryred: absolute experiment
Fedor May Allan (2008)
Čížek Horáček Sergenton Popović Allan Domcke Leininger GadeaPhys. Rev. A 63 (2000) 062710
dissociative attachment cross section drops when a new vibrational excitation channel opens
26
to remember:
long range (dipole) attraction „nonlocal phenomena“
Vibrational Feshbach Resonancesthreshold peaks in VElarge CS and steps in DEA
27
CO2
has no dipole moment – is it like H2 ?
Fermi Resonance
the (1000) and (0200) vibrations mix
true states: {(1000) + (0200)}
(Fermi dyad) {(1000) - (0200)}
two Raman lines
28
Excitation of the Fermi – split states is highly selective!
Allan, Phys. Rev. Lett. 87 (2001)
virtual state * shape resonance
Exciting the Fermi-dyad in CO2
29Allan, (2011, in print)
Cross section for exciting the topmost member of the tetrad {(3000), (2200), ... }
30
Similarity of vibrational cross sections in CO2 and HF
D D
31
Potential curves of CO2 and HF
Physica Scripta (2004)
bending
32Allan, J. Phys. B (2002)
33
FIG. 3. Contour plots of the wave functions for the twocomponents of the Fermi dyad in O-C-O angle. The thick line marks the seam where the anion and neutral surfaces cross. Top panel: upper member of dyad; bottom panel: lower member of dyad.
Vanroose et al. PRL 2004
Understanding the selectivity within the dyad
34
Until now: effects due to long range electron binding: • threshold peaks in VE• sharp structures in VE cross sections• Vibrational Feshbach resonances• large cross sections and threshold peaks in DEA• steps in DEA cross section• theory: nonlocal theory essential• existing theory: one dimension (diatomic or pseudodiatomic)
Next: effects due several dimensions of nuclear motion:
• symmetry-lowering due to vibronic coupling
• anion needs to distort in order to dissociate
• theory: several dimensions of nuclear motion essential
35
theory:S. T. Chourou and A. E. Orel 2009
experiment:O. May, J. Fedor, B. C. Ibanescu and M. Allan 2009
isotope ratio:
experiment : 14.4
theory at 0 K : 28.9
theory at 333 K : 17.9
but :
theoretical cross section nearly 2× too large
36
Dissociative Electron Attachment to AcetyleneS. T. Chourou and A. E. Orel PRA 2008
37
Dissociative Electron Attachment to AcetyleneS. T. Chourou and A. E. Orel
38
Chlorobenzene
Skalický, Chollet, Pasquier, Allan, Phys. Chem. Chem. Phys. 2002
39
Chlorobenzene
- the * resonances act as doorway states into the * resonance
- no activation barrier ← symmetry lowering ← vibronic coupling
Skalický, Chollet, Pasquier, Allan, Phys. Chem. Chem. Phys. 2002
ring breathing C-Cl stretch
40
Two families of DEA:
Puzzle: mechanism in formic acid ? • both * shape resonance and polar O-H bond
HBr• no shape resonance
• peak at threshold
• steps
• nonlocal theory required
H-C≡C-H• * shape resonance
• peak at resonance
• LCP sufficient
• inherently multidimensional
C
O
O
H
H
HCOOH + e HCOO + H
41
Vibrational excitation of formic acid
42
Vibrational excitation of formic acid
- cusps, like HCl, HBr, HF
43
HCOOH + e HCOO + H : approach I
theory: R-matrixG. A. Gallup, P. D. Burrow and I. I. Fabrikant PRA 2009
experimentA. Pelc, W. Seiler, P. Scheier, N. J. Mason, E. Illenberger and T. Märk 2003 & 2005
44
* anion * anionneutralC
O
O
H
H
approach II
45
Dissociation of formic acid anionon the valence * shape resonance potential surface
DFT B3-LYP 6-31G*
Isotope effect expected for D substitution on C-H
46
Isotope effect
D. Kubala, O. May, M. Allan, 2011
47
Formic acid is a prototype for biomolecules : forms hydrogen bonds !
M Allan, Phys. Rev. Lett. (2007)
48
Similar situation in other biomolecules : uracil
49
Family III: higher energies
On the complexity of dissociation via core-excited Feshbach resonances
in polyatomic molecules
50
Feshbach resonances
51
photoelectron spectra are useful in predicting Feshbach resonances
Bogdan Ibanescu 2007
52
O-C bond does not dissociate !
Bogdan Ibanescu 2007
53
Bogdan Ibanescu 2007TD-DFT, pbe0/6-311++g(3df,3p), geometry: DFT b3lyp/6-311+g(2df,2p)
Rydberg states: potential curves
54
a recent example : Pt(PF3)4
(a FEBIP precursor)
55
Pt(PF3)4 : vibrational states
56
Pt(PF3)4 : fragmentation
O. May, D. Kubala, poster Mo 038
57
Atoms
great success of theory !
58
Absolute cross sections for excitation of the Ne (2p53s) states at θ = 180°.
M Allan, K Franz, H Hotop, O Zatsarinny and K Bartschat 2008
Ne
59
Some research groups
active in electron
collisions
60
Martin, Burrow, Cai, Hunting, Sanche, Phys. Rev. Lett. 2004
Sanche and co-workers:slow electrons damage DNA
Science, 2004
61
Sherbrooke, Canada
• Léon Sanche
• biomolecules, surfaces, theory
Lincoln, Nebraska
• Paul Burrow, Gordon Gallup, Ilya Fabrikant
• DEA, theory
Davis & Berkeley, CA
• Ann Orel, Tom Rescigno, Bill McCurdy : theory
• H. Adaniya : DEA experiment - COLTRIMS
Belfast
• Tom Field; Gleb Gribakin
• ToF DEA, biomolecules; theory
Kaiserslautern
• Hartmut Hotop
• ultrahigh resolution, ultralow energy
62
Gdansk
• Mariusz Zubek, Marcin Dampc
• cross sections, magnetic angle changer
Innsbruck
• Paul Scheier, Tilmann Märk, Stefan Denifl
• biomolecules, electron collisions in He nanodroplets
Berlin
• Eugen Illenberger
• DEA, biomolecules
Open University, Milton Keynes
• Nigel Mason, Jimena Gorfinkiel
• European leadership, theory
Bratislava, Slovakia
• Stefan Matejcik
• DEA
University of Podlasie, Poland
• Janina Kopyra
• DEA, electron transport
63
Prague, Charles University
• Jiří Horáček, Martin Čížek, Karel Houfek (+ Wolfgang Domcke)
• theory
Prague Heyrovský Institute
• Petr Čársky, Roman Čurik
• theory
Orsay
• Robert Abouaf, Roger Azria, Ann Lafosse
• cross sections, surfaces
Belgrad
• Bratislav Marinkovic, Aleksandar Milosavljević, Zoran Petrovic
• cross sections
Roma
• Franco Gianturco, Isabella Baccarelli
• theory
Bremen
• Petra Swiderek
• electron collisions with molecules in cold matrices
64
Tata Institute, Mumbai
• E. Krishnakumar, S. V. K. Kumar, V. Prabhudesai
• DEA experiment : velocity slice imaging
Brazil
• Marco Lima, M.H.F. Bettega, Romarly F. da Costa, M.-T. Lee and Ione Iga
• theory, high energy experiment
Island
• Oddur Ingólfsson
• experiment, DEA
Korea
• Hyuck Cho
• magnetic angle changer, cross sections
Aarhus
• David Field, Oksana Plekan
• very low energies, ferroelectricity
London
• JonathanTennyson
• R-matrix theory
65
Drake University
• Klaus Bartschat, Oleg Zatsariny
• theory
Caltech
• Vince McKoy, Carl Winstead
• theory
Fullerton, CA
• Morty Khakoo
• cross sections
Australia
• Igor Bray, Dmitry Fursa, Laurence Campbell
• theory
Australia
• Stephen Buckman, Michael Brunger, ...
• transient molecules, metastable atoms, positrons
Tokyo
• Hiroshi Tanaka
• cross sections
66
Where do we find
electron – driven chemistry and physics?
67
- Outer space
- Ionosphere: northern light etc.
- Industrial plasmas- semiconductor manufacture- flat displays
- plasma displays- LCD display manufacture- back-lighting: Xe excimer
- surface modification- hydrophilic- hydrophobic- shrink-proof wool- milk packaging- …
- waste disposal- satellite engines
Electron – Driven Chemistry: gas phase
68
· Low Temperature Plasma Science and Technology has a history and future of robust, interdisciplinary science challenges whose resolution provides immediate and long term societal benefit.
ROBUST SCIENCE,SOCIETAL BENEFIT
slide by Prof. Mark J. KushnerUniversity of Michigan
Institute for Plasma Science & Engr.with permissionGEC2010
Ref: Adapted from “Plasma Science: Advancing Knowledge in the National Interest”, US National Research Council, 2007.
69
Angle-integrated cross section for electron-impact excitation of the (6s6p) 3P0
o state of mercury from the (6s2) 1S0 ground state.
Resonance in Hg
70
SUCCESS AT CONTROLLING f(): PLASMA LIGHTING
· Annual US electrical power consumption: 3.5 x 1012 kW-Hr
· Electrical power expended in lighting: 22% - in fluorescent lamps: 9%
· 35 1-GWe power plants are used to excite a single multiplet of Hg in fluorescent lamps.http://www.eia.doe.gov/cneaf/electricity/epa/epates.htmlhttp://antwrp.gsfc.nasa.gov/apod/ap970830.html http://www.eere.energy.gov/buildings/info/documents/ pdfs/lmc_vol1_final.pdf
· Optimizing f() in plasma lighting by 0.1 eV translates into three 1-GWe plants.
· This is an incredible accomplishment and mastery of discharge physics.
GEC2010
slide by Prof. Mark J. Kushner
University of MichiganInstitute for Plasma Science & Engr.
with permission
71
validate theory by comparing absolute (differential) cross sections for :- elastic scattering- vibrational- electronic- DEA
Conclusions
c.f. photochemistry
72
Where are we ?
- Much remains to be done
Electron-driven physics and chemistry
theory
DEA: threshold phenomena
diatomics OK
polyatomics ?
multidimensional phenomena
H-C≡C-H ; LCP only
Feshbach/shape reson.Rydberg/valence conical intersectionsH2O, CO2 ; only beginning
elastic scattering vibrational excitation electronic excitation
experiment - full set of absolute cross sections measured for only few molecules
- DEA : angular distributions
- transient molecules (CF2 , metastables)
- surfaces, liquids
73
Rainer Dressler
Louis Neuhaus
Bruno Albrecht
Knut Asmis
Christophe Bulliard
Olivier Schafer
Anne-Christelle Sergenton
Duška Popović
Momir Stepanović
Emil Brosi
Paul-Hervé Chassot
Olivier Graber
Tomáš Skalický
Svetlana Živanov
Bogdan Ibanescu
Olivier May
Juraj Fedor
Dušan Kubala
Wolfgang Domcke
Jiří Horáček
Martin Čížek
Karel Houfek
Roman Čurik
Petr Čársky
Jean-Pierre Gauyacq
Arvid Herzenberg
Ilya I Fabrikant
Tom Rescigno
Ann Orel
Bill McCurdy
Klaus Bartschat
Lorenz Cederbaum
Gleb Gribakin
Hartmut Hotop
74
75
Spin-orbit components of the NO ground electronic term
Allan, Phys. Rev. Lett. (2004)
76
Br– + H HBr( ,J) + e–(E)
e–(E) + HBr H + Br–
dissociative electron attachment (DEA)
associative electron detachment (AED)
related by the microscopic reversibility, but AD probes much higher J
and the reverse process
sideline : Associative Electron Detachment
77
- Collision parameter b determines J
- energy of departing electron carries information about final , J
- this permits recording cross section as a function of J for each !
sideline : Associative Electron Detachment
78
Interchannel coupling in associative detachment dramatically influences product state distribution
Živanov, Allan, Čížek, Horáček, Thiel, Hotop, Phys. Rev. Lett. (2002)
associative electron detachment
top related