Resonances & Reaction

Dynamics
Lecture on 22/01/2014

Wednesday 22 January 14
 Centrifugal Barrier
A A A
For collision reactions, one important
factor to account for is the orbital
angular momentum. This is not the
quantum mechanical orbital angular B B B
momentum, but a classical one. The
orbital angular momentum that we will
look in the frame work of collision
reaction is the one that corresponds to
line-of-centers.

From the figure on the right, it is obvious

that for a head-on collision (where b=0),
the line of centers orbital angular
momentum is zero.

Thus, this angular momentum is present

for all the cases where b>0
Wednesday 22 January 14
 Let us now try to formulate an expression for orbital
angular momentum of line-of-centers

L=R⇥p relative linear momentum

vector separating A & B

|L| = |R ⇥ p| = |µR ⇥ vrel | = µvvel R sin ✓

A
R vrel magnitude of
orbital angular
b momentum
B
✓
depends on b,
and relative
) |L| = µvvel R sin ✓ = µvvel b velocity!
Wednesday 22 January 14
 • We can neglect the contribution of
A
quantum mechanical orbital angular
momentum (usually these values are R
small)
B
• Then, total orbital angular momentum
of reactants ≈ L

Then the total relative kinetic energy is KE due to change in LOC

given by 2
(remember: we don’t need CM velcocity 1 2 |L|
Krel = µṘ +
as it is any way not available for reaction) 2 2µR2
KE orbital angular momentum of LOC
This is also called centrifugal kinetic
energy, Kcent
2
|L| 1 2 b2 b2
Kcent = 2
= µvvel 2 = Ec 2
2µR 2 R R
Wednesday 22 January 14
 If we consider reactive collisions as elastic collisions,
angular momentum is conserved during the course
of collision (similar to the conservation of center of
mass velocities). That is,
angular momentum of reactants=angular momentum
of products.

Due to the (total) angular momentum

conservation, the Kcent cannot be taken
out from the total kinetic energy of
molecule for chemical reaction (as it has
to conserve!)
Wednesday 22 January 14
 • In other words, Kcent is not available for surmounting the
activation barrier. This has the effect of reducing the total
energy available!

• We can think of an effective potential acting during the collision

reactions: Ue↵ (R) = U (R) + Kcent

high |L| high|L|

U (R) U (R)
|L|=0 |L| =0

Such effect will result in increasing it may create barriers for cases
the effective barrier as shown above where there is no activation barriers
further slowing down the reaction on the potential energy surface

Such barriers are called centrifugal barriers

Wednesday 22 January 14
 Quantum Bottleneck States
Quantized
levels will be
present in However, along a
any bound reaction coordinate, such
states on the quantization doesn’t 300
potential occur.
250

energy 200
300
surface
Perpendicular to the 150
250
200
reaction coordinate 100
50
150 quantum states do 0
100 exist : These are called-50
50
0 Quantum Bottle -100
-50 neck States(QBS) 0.5
1
1.5
0.5 2 r(DF)
1
1.5 2.5
2
r(DD) 2.5 3
Wednesday 22 January 14
 See the figure at the right side. red lines are
showing path taken by the reactants/products
during the reaction mapped on the top of the
potential energy surface. You could clearly see
the vibrations perpendicular to the dotted lines
(minimum energy pathway/reaction
coordinate). No such vibrations are present in
the direction of the dotted line)

• Energy available for the motion along the reaction coordinate (or
the minimum energy pathway), doesn’t (easily) flow or get
distributed to the vibrational motions or rotational motions
perpendicular to it. This is also true vice versa. Or in otherwords,
the energy that is available for the vibrational motion
perpendicular to the minimum energy pathway is not accessible
for chemical reaction (remember: chemical reaction is nothing
other than motion along the minimum energy pathway).
Wednesday 22 January 14
 Let us consider a case where there is centrifugal barrier /
potential energy barrier that needs to be overcome by the
reactants as shown in the figure below.

QBS • Let us also consider a case where energy available for

the reaction (Ec) is in resonance with this barrier (Ea).
Ec
Then molecules will loose all its translational energy
Ea while reaching the top of the barrier.
Ec = Ea

• This results in zero velocity at the top of the

transition state, resulting in slowing down the reaction
for a few femtoseconds; the transition state structure
will get some life time.

• This will happen only if QBS (which are perpendicular

to it) do not supply energy for the translational
motion along reaction coordinate. Such process can
take a few tens of pico/femto seconds, giving a longer
life time for the transition state structure
Wednesday 22 January 14
 • This is a situation similar to the case of
Br2+O reaction, where a stable
intermediate is formed, which has certain
definite life time. But the transition state life
time due to QBS very small.
• Similar to the case of B2+O, formation of
stable intermediates result in forward
scattering! (which would otherwise only
backward scatter, as expected for small b
reactions)

H2+H reaction is a good example!

Wednesday 22 January 14
 (e-mail: fujisawa@will.brl.ntt.co.jp). readily reproduced
Quantum dynamical processesbynear
the quantum calculations.
the energy barrier However
that
scattering observed in the H þ D2 reaction3–5 at higher separates collisionalreactants the forward
from peak to specific
products dynamical
influence behaviour
the detailed mecha-require
energies. The characteristics of the forward scattering H2nism by which theoretical
elementaryanalysis.
chemical reactions occur. In fact, these
NATURE | VOL 419 | 19 SEPTEMBER-products
are unique. First, it is clear that the forward scattering H2processes
products
2002 | can www.nature.com/nature © 2002
change the product scattering behaviour from that
..............................................................
are significantly colder rotationally, with mainly H2( j 0 ¼expected 1) popu-from simple collision considerations, as seen in the two
classical reactions F 1 H2 ! HF 1 H and H 1 H2 ! H2 1 H
Forward scattering due to slow-
lated, than the backwards and sideways scattering products. Second,
the angle range of the observed forward scattering peak is extremely
and their isotopic variants. In the case of the F 1 HD reaction,
the role of a quantized trapped Feshbach resonance state had
down of the intermediate in the
narrow. Experimental characteristics of the forward scattering
including the rotational distribution and the angular width
been directly peak determined1, confirming previous conclusions2 that
can beresonances cause state-specific forward scattering of
Feshbach
H 1 HD ! D 1 H reaction
readily reproduced by the quantum 2 calculations. However,product to assign molecules. Forward scattering has also been observed in
the forward peak to specific dynamical behaviour requires thefurther H 1 D2 ! HD 1 D reaction3,4 and attributed to a time-
theoretical
Steven A. Harich*, analysis.Dongxu Dai*†, Chia C. Wang*‡, Xueming Yang*†§, delayed mechanism3,5–7. But despite extensive experimental8–12
Sheng Der Chaok{ & Rex T. Skodjek{ and theoretical13–18 investigations, the details of the mechanism
remain unclear. Here we present crossed-beam scattering experi-
* Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan
ments and quantum calculations on the H 1 HD ! H2 1 D
† Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian,
China
reaction. We find that the motion of the system along the reaction
‡ Department of Chemistry, National Taiwan University, Taipei, Taiwan coordinate slows down as it approaches the top of the reaction
§ Department of Chemistry, National Tsing Hua University, Hsinchu,barrier, Taiwan thereby allowing vibrations perpendicular to the reac-
k Institute of Molecular Science, Myodaiji, Okazaki 444-8585, Japantion coordinate and forward scattering. The reaction thus pro-
7
{ Department of Chemistry and Biochemistry, University of Colorado, ceeds,
Boulder,as previously suggested , through a well-defined F
Colorado 80309, USA ‘quantized bottleneck state’ different from the trapped Feshbach S
resonance states observed before.
............................................................................................................................................................................. o
Quantum dynamical processes near the energy barrier In this thatwork, we studied the H þ HD ! H2 þ D reaction experi- th
separates reactants from products influence the detailed mecha-using the H(D)-atom Rydberg time-of-flight (HRTOF) tr
mentally
nism by which elementary chemical reactions occur. In fact, technique, these developed in refs 12 and 19. We measured time-of-flight e
processes can change the product scattering behaviour from (TOF)that spectra of the D-atom products at different laboratory d
expected from simple collision considerations, as seen in the two angles at the collisional energy of 1.200 eV. The TOF s
scattering
classical reactions F 1 H2 ! HF 1 H and H 1 H2 !spectra H2 1 measured H are then converted to the centre-of-mass product m
and their isotopic variants. In the case of the F 1 HDtranslational
the role of a quantized trapped Feshbach resonance tional
1
forward scattering
reaction, energy distributions. Different H2-product rovibra- u
state had
2
states can be resolved clearly in this experiment. From these P
been directly determined , confirming previous conclusions distributions, that relative quantum state-specific differential cross- c
Feshbach resonances cause state-specific forward scattering sectionsof(DCS) are obtained. On the basis of this measured data, th
product molecules. Forward scattering has also been observed in
a full three-dimensional (3D) product contour plot is constructed b
the H 1 D2 ! HD 1 D reaction and attributed toand 3,4
a time-
shown in Fig. 1. One of the most interesting observations is the m
3,5–7 8–12
delayed
Wednesday mechanism
22 January 14 . But despite extensive experimental forward scattering peak seen in Fig. 1, similar to the forward e
 Molecular beam studies of the F+H2 reaction
Molecular beam
D. M. Neumark, studies
A. M. Wodtke, ofRobinson,
G. N. the F+H2 C. C.reaction
Hayden, and Y. T. Lee
D. M. Neumark, A. M. Wodtke, G. N. Robinson, C. C. Hayden, and Y. T. Lee
3058 Neumark et a/.: The F + H2 reaction
Citation: The Journal of Chemical Physics 82, 3045 (1985); doi: 10.1063/1.448254
View online:
Citation: The http://dx.doi.org/10.1063/1.448254
Is
Journal of Chemical Physics 82, 3045 (1985); doi: 10.1063/1.448254
1.84 keal/mole the
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/82/7?ver=pdfcov
View online: http://dx.doi.org/10.1063/1.448254
forward
F+n-H2-->HF+H. 2.74 keal/mo
Published by the AIP Publishing
scattering in
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/82/7?ver=pdfcov
v=1- this
Published by the AIP Publishing
case due to
/
/
/ /
/ /
/ I
/ I

Quantum
I I
I I
, I
I
I

,,/
I

Bottleneck
I
I
I

o·c-: O'''!--,-+--+1
,, FIG. 18. Center-of-mass \

velocity flux contour map States?

\
,, \
\
\
for F + P-H2' 1.84 kcal/
\ \
\ \
\ \
\
\ mol, with three-dimen- \
\
\ \
sional perspective. Lines
Theoretical calculations
\

''-''- are spaced linearly along '" .....

'"
'"
the 3D contour according
showed that it is due to
to scattering intensity.

quantum effects (like

tunneling)

Wednesday 22 January 14
 Reaction resonances, or transiently stabilized transition-state structures, have proven highly
20. M. A. Henderson, S. O. Tapia, M. E. Castro, Fara. Disc. 32. E. Hendry, F. Wang, J. Shan, T. F. Heinz, M. Bonn, Phys.
challenging to capture experimentally. Here, we used the highly sensitive H atom Rydberg tagging the FH2jsamp ph
114, 313 (1999). Rev. B 69, 081101 (2004).
time-of-flight
21. S. P. Bates,method to conduct
M. J. Gillan, G. Kresse, aJ. crossed
Phys. Chem.molecular
B 102, beam scattering
33. H. Decornez, study of the F þ H
S. Hammes-Schiffer, Y HF
J. 2Phys. þ AH104,ture 3of
Chem. the
Novemb
This problem was solved in 2006:
reaction
2017with full quantum-state resolution. Pronounced forward-scattered
(1998). 9370 (2000). HF products in the photoelectro
10.1126/s
v¶ 0 2 vibrational state were clearly observed at a collision energy of 0.52 kcal/mol; this was attributed and Manolo
to both the ground and the first excited Feshbach resonances trapped in the peculiar HF(v¶ 0 3)-H¶ Despite m
vibrationally adiabatic potential, with substantial enhancement by constructive interference between this system
Observation of Feshbach Resonances
the two resonances.
F þreso
reaction HD
excitatio
scattering ex
The most well-studied example for dynam- over,unambig

Din the F þ H Y HF þ H Reaction

ynamical resonance in chemical reac-
tions (1) has attracted great attention ical resonance is the F þ H2 Y HF þ H re- the SW-PES
from both experimentalists2and theoret- action, which is also known to be the main
seriou
oretical
that this
1,3 1 1 1
Minghui
icians (2–5)Qiu,over *the Zefeng
past 30 Ren,
years.* LiInChe, Dongxu
general, Dai,1 Steve
pumping step forA.theHarich, 1
Xiuyanlaser.
HF chemical Wang, 1
Theo- 2StateNeumar Key La
Center forstat
The
Xueming
the transition state1†isChuanxiu
Yang, an energy Xu, maximum4
Daiqian Xie,4†
along Magnus
retical Gustafsson,
predictions 5,6
Rex resonance
of a reaction T. Skodje,in 5,6 tion
the Institute of Che
1,2,7 1,2,7 photode
Zhigang
the reactionSun,coordinate,Dong andH.soZhang
it does not † per- F þ H2 reaction were first made in the 1970s Dalian, Liaonin
sist as a discrete structure. However, in special (6–9). In a landmark crossed-beams experiment Physics, tumDalian
me
4
Reaction
cases, resonances,
a reaction complex or transiently stabilized transition-state
in the transition-state on the F þ structures,
H2 reactionhave proven
in the highly
collision energy PES ofledT
Institute
challenging
region can be to capture experimentally.
transiently Here, we used
trapped in vibrationally rangetheofhighly
0.7 tosensitive H atom
3.4 kcal/mol byRydberg
Lee andtaggingco- Department
the FHof2
Jiangsu 21009
time-of-flight
adiabatic wells method
along the to reaction
conduct coordinate.
a crossed molecular
A workers beam(10,scattering
11), a study of the F þ H2peak
forward-scattering Y HF ture Scien
forþ HMolecular of
reaction with
transiently full quantum-state
trapped resolution.
state along the reaction Pronounced
coor- the HF(v¶ 0 3) product HF
forward-scattered wasproducts
clearly in the
observed photoele
Taiwan. 6
Depart
v¶ 0 2 in
dinate vibrational state were region
the transition-state clearly isobserved
normally at a collision
and was energy of 0.52
attributed kcal/mol;resonance.
to a reaction Later sity ofand
this was attributed Colorado
Ma
Computational
called
to botha the
dynamical
ground and resonance
the firstorexcited
a Feshbach
Feshbachtheoretical
resonancesstudies
trappedusing bothpeculiar
in the HF(v¶ 0 3)-H¶ SingaporeDesp
the quasi-classical
1192
resonance.
vibrationally Dynamical resonance with
adiabatic potential, (or substantial
reaction enhancement
trajectory method (12) and the
by constructive quantum between
interference me- this syst
*These authors
resonance) thus constitutes an extremely sensi- chanical scattering method (13) on the Stark- †To whom
the two resonances. reaction
cor
tive probe of the potential energy surface (PES) Werner PES (SW-PES) (14), however, did not xmyang@dicp scatterin
of a chemical reaction.
resonance in chemical reac- confirm thismost
conjecture. In a recent studyforofdynam-
the dicp.ac.cn

D
ynamical The well-studied example over, se
tions (1) has attracted great attention ical resonance is the F þ H2 Y HF þ H re- the SW-
from both experimentalists and theoret- action, which is also known to be the main
1440 10 MARCH 2006 VOL 311 SCIENCE www.sciencemag.org 1
icians (2–5) over the past 30 years. In general, pumping step for the HF chemical laser. Theo- 2State Ke
Center fo
the transition state is an energy maximum along retical predictions of a reaction resonance in the Institute o
the reaction coordinate, and so it does not per- F þ H2 reaction were first made in the 1970s Dalian, L
sist as a discrete structure. However, in special (6–9). In a landmark crossed-beams experiment Physics, D
4
Wednesday 22 January 14 Institute
 forward scattering was
seen majorly for HF(v=3)
and also HF(v=2)

Wednesday 22 January 14
 Let us consider the formation of centrifugal
transiently trapped structure along the barrier/
reaction coordinate as shown in the
tunneling potential energy
figure at the right. These barriers may Ec barrier
arise from the centrifugal & potential
energy barriers

Let us also consider that there exits a

vibrational/rotation state for this transiently trapped
transient species. along the reaction
coordinate (life time of
When collision energy become resonant few fs)
with the energy levels of the transient
species, then the reactants can tunnel
(depending on the energy level, Such a resonance with the quantum states of
molecules etc.; lighter molecules are the transiently trapped intermediate is called
easy to tunnel; tunneling usually happen Feshbach resonance (or dynamic
close to the barrier) resonance)

Wednesday 22 January 14
 centrifugal
barrier/
tunneling potential energy
Ec barrier
Due to tunneling, reactants form
the transient intermediates even
with collision energy lower than
the potential energy barrier for
the reaction. transiently trapped
along the reaction
coordinate (life time of
few fs)

Wednesday 22 January 14
 In the case of F+H2 reaction, it was identified
that a weakly bound (HF...H) complex form
during the reaction, and has a definite life time
RTS

This complex
has similar
behavior of HF,
but coordinated
weakly to the H
atom that will be
cleaved from the
H2
g. 3. (A) Collision energy–dependent DCS for
e forward-scattering HF(v¶ 0 2) product. A Fig. 4. Schematic diagram showing the resonance-mediated reaction mechanism for the F þ H2 reaction

sonance-like peak is clearly observed at the
llision energy of 0.52 kcal/mol. The solid circles
e the experimental data, and the solid line is
e calculated theoretical result. (B) The total DCS
the HF(v¶ 0 2) product and the DCS con-
butions to the HF(v¶ 0 2) product from both the
reactant
with two resonance states trapped in the peculiar HF(v¶ 0 3)-H¶ VAP well. The 1D wave functions of the
intermediate
two resonance states are also shown. The (003) state is the ground resonance state; the (103) resonance
is the first excited resonance state. Calculated van der Waals states for the lower VAPs are also shown.
F+ H2 HF.....H
OP, overtone pumping; Eb, barrier height; Ec, collision energy.

ound and the 22

excited resonance partial waves at agreement shows clear progress from simulations HF(v¶ 0 2) forward scattering, but the ground
Wednesday January 14
 relative energy of F+ H2 reactants are in resonant
with v’=3 energy levels of HF...H complex, former will
tunnel to form HF...H with v’=3).
RTS

It has also found by

theoretical
calculations (you
don’t need to know
how), potential
energy surfaces of
v’=2 and v’=3 couple
each other. By this,
g. 3.some HF...H
(A) Collision withDCSv’=3
energy–dependent for
canpeak“leak” to v’=2
e forward-scattering HF(v¶ 0 2) product. A Fig. 4. Schematic diagram showing the resonance-mediated reaction mechanism for the F þ H reaction
2

and the solid line is is the first reactant intermediate

sonance-like is clearly observed at the with two resonance states trapped in the peculiar HF(v¶ 0 3)-H¶ VAP well. The 1D wave functions of the

e the experimental data, state

llision energy of 0.52 kcal/mol. The solid circles two resonance states are also shown. The (003) state is the ground resonance state; the (103) resonance
excited resonance state. Calculated van der Waals states for the lower VAPs are also shown.
e calculated theoretical result. (B) The total DCS
the HF(v¶ 0 2) product and the DCS con-
butions to the HF(v¶ 0 2) product from both the
F+ H2
OP, overtone pumping; Eb, barrier height; Ec, collision energy.
HF.....H
ound and the 22
excited resonance partial waves at agreement shows clear progress from simulations HF(v¶ 0 2) forward scattering, but the ground
Wednesday January 14
 Because of this, HF...H intermediates are formed with v’=3 and
v’=2 (with varying amount depending on the coupling of
potential energy surface). [Details on this is beyond the purpose
of this course]

Due to the stability of the HF...H intermediate (as also indicated

by the shallow potential energy wells for each of the vibrational
states in the figure before), we can expect that the HF...H
molecules with v’=3 and v’=2 could result in backward and
forward scattering

This is exactly what is seen in experiments (see 5 slides before)

Wednesday 22 January 14
 Note: HF...H in a v’ vibrational state will always
decay to HF molecule with v’ state.

This is because, within the molecular beam

setup, HF molecules formed are not undergoing
collisions till they reach the detector.

Due to lack of collisions with in the HF

molecules, they retain their vibrational levels;
thus v=2 & v=3 are highly populated.

This is the reason for a non-Boltzmann

distribution

Wednesday 22 January 14
 Similar observations were also made
for D2+F and DH+F reactions.
Molecular beam studies of the F+D2 and F+HD reactions
D. M. Neumark, A. M. Wodtke, G. N. Robinson, C. C. Hayden, K. Shobatake, R. K. Sparks, T. P. Schafer,
and Y. T. Lee

Citation: The Journal of Chemical Physics 82, 3067 (1985); doi: 10.1063/1.448255

•
View online: http://dx.doi.org/10.1063/1.448255
Note:View
as you notice
Table of from
Contents: the right hand 3068
http://scitation.aip.org/content/aip/journal/jcp/82/7?ver=pdfcov Neurnark et al.: The F

side figure onby the

Published energy
the AIP Publishinglevels of DF
HF(v=3) F+H
and HF, the levels v<3 are only F+HD

I
T
DF(v=4)

accessible for low energy collisions, f 32.53

3168
while for HF v<3 are only accessible. v=3 v=2

This is due to the difference in mass of

D and H.
I
v=2
24.15
3125 I22.16
L\E=
3186
---r v=1
32.07

• I 32.84

I
16.36
Thus, if D2+F also shows Feshbach v=1
resonance, then we can expect similar I8.31 11.33

forward scattering for v=4 &/ v=3 of v=ol

v=O

DF AG. 1. Energetics of the F + H2 , F + D2 , and F + HD reactions. AJI

values are in kcal/rnol. H2 , D2 , and HD are in their lowest internal
states (v = 0, J = 0).

studied in several trajectory calculations. 9- 11 The most

Wednesday 22 January 14 interesting result, that the HF/DF branching ratio from
 := l)/(v = 3) ratio increased as the collision energy was
raised. Figure 18 shows that the v = 2 and v = 1 products
increase at the expense of v = 3 and v = 4 as the energy
However, forward resonance is not seen for neither v=4 or any other
is raised. The trend in the kinetic energy dependence of
v<4! However, forward scattering is seen for v=4 when collision
the (v = energy 3) ratio to
2)/(v =is increased agrees with the(see
3.32 kcal/mol temperature-
the figures below).
8
dependent chemiluminescence results Why? but not with an
earlier chemical laser study6 which showed a significant

F+02->OF+O, 3.32 keal/mole

F+D2-->DF+D, 1.82 kcal/mole

-',
",

""','\
FIG. 14. Center-of-mass
, velocity flux contour map FI
'.\ for F + D 2 , 1.82 kcal/mol. ve
\
\
\
Lines are spaced linearly for
along the 3D contour ac-
\
\
\
cording to scattering in-
\
\ tensity.
\
\
\

\"",
'"
Wednesday 22 January 14
 DF...D
intermediate
Theory and experiments hinted
is formed
on the occurrence of Feshbach
resonance at collision energy
3.32 kcal/mol. This means,
high value of |L| Feshbach resonance is occurring
only for high values of collision
energy. This can be ascribed to
the fact that, at high values of
collision energy, values of |L| is
low value of |L| such that the corresponding
centrifugal barriers create
transiently stabilized DF...D
complex. For low values of
DF...D collision energy, and thus low |L|,
intermediate centrifugal barriers are such
transient species are not formed
is not formed (as indicated in the figure here)

Wednesday 22 January 14
 Mysteries of Lee’s Experiments

1. Why the D2+F reaction is rebound?

✔
2. Why there is a forward flux seen when
collision energy is increased? Why this is only
observed for v=4?
✔
3. Why is the population of HF products higher
for v=3 (and v=4 for some collision energy)?

Wednesday 22 January 14
✔