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J. CHEM. SOC. FARADAY TRANS., 1995, 91(4), 575-596 575

FARADAY RESEARCH ARTICLE

Reactive Scattering of Atoms and Radicals
Michele Alagia, Nadia Balucani, Piergiorgio Casavecchia," Domenico Strangest and
Gian Gualberto Volpi*
Dipartimento di Chimica, Universita di Perugia ,06100 Perugia , Italy
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Dynamical studies of elementary gas-phase bimolecular reactions have progressed significantly during the last
few years owing to advancements in molecular beam and laser techniques as well as in theoretical method-
ologies. In this article we give a brief overview of the recent progress in the field of reaction dynamics and then
survey recent work from our laboratory on reactions of atoms and radicals with simple molecules by the
crossed molecular beam scattering method using mass-spectrometric detection. Emphasis is on three-atom
(A + BC) and four-atom (AB + CD) reactions for which the interplay between experiment and theory is the
strongest and the most detailed. Reactive differential cross-sections for the three-atom CI + H, and four-atom
OH + H, and OH + CO reactions are presented and compared with the results of quasiclassical and quantum-
mechanical scattering calculations on ab initio potential-energy surfaces in an effort to assess the status of
theory versus experiment. The reaction dynamics of electronically excited atoms are discussed too; the effect of
electronic excitation on the reaction dynamics of atomic oxygen is examined using the reaction O(3P,'D) + H,S
as an example.

1. Introduction theory and experiment. Theoretical studies have been con-

cerned with developing accurate (model, semiempirical and
The study of elementary chemical reactions at the level of
ab initio) PESs, as well as techniques for scattering calcu-
individual atoms and molecules constitutes the essence of
lations on these surfaces, with the aim of acquiring a deeper
chemical reaction dynamics and is nowadays one of the
insight into reaction dynamics.l4 The calculation of accurate
major patterns of inquiry in chemical kinetics. '-' Molecular
ab initio PESs represents a true bottleneck in the field of
beam and laser spectroscopic techniques permit experiments
chemical reaction dynamics. In fact, once the PES is known,
which are able to give detailed information about the
all the experimental observables can be calculated, at least in
dynamics of elementary gas-phase chemical reactions. Funda-
principle. This is a reality, today, for simple reactions involv-
mental questions connected with product energy partitioning,
ing three atoms where theoretical calculations of dynamical
product angular distribution, the effect of reagent quantum-
observables often guide experimental efforts, and is becoming
state distribution and the evolution from reactants to pro-
feasible for four-atom reaction systems as well. However,
ducts can be addressed very closely and in most cases
semiempirical methods for calculating PESs are still very
detailed answers can be provided.
important. In fact, although PESs, to an ever higher degree of
The history of the field of reaction dynamics goes back to
accuracy, are being proposed for relatively simple prototype
1928, when the advent of quantum mechanics permitted a systems, a more widespread procedure still follows the pre-
detailed picture of the microscopic rearrangement of atoms
scription of Polanyis in carrying out classical trajectory cab
leading to chemical reaction^.^* Since then, the fundamental
culation on LEPS (London-Eyring-Polanyi-Sato) type
idea in reaction dynamics has been that reactive collisions
surfaces so as to optimize the surface parameters in order to
can be described and understood by considering the motion
match the experimental results. Note that since the early
of the system over a potential-energy surface (PES). The first
days, but especially since the 1960s and 1970s, classical trajec-
classical trajectory study of the dynamics of a chemical reac-
tory studies have contributed enormously to our understand-
tion was carried out as long ago as 1936 by Hirschfelder,
ing of the dynamics of atom + diatom reactions by
Eyring and T ~ p l e y ' on
~ the hydrogen exchange reaction
connecting measured properties to features of the PES and
+
H + H, -+ H, H on the London potential-energy
reaction kinematics; this work led to the so-called 'Polanyi
and since then, the interpretation of most reaction dynamic rules' 5.9.14
experiments has been based on the concept of adiabatic
The experimental techniques usually employed for gas-
motion on a single electronically adiabatic PES, although
phase reaction dynamics studies fall essentially in two cate-
failure of the Born-Oppenheimer approximation can occur.
gories : crossed molecular beam (CMB) methods and
Experimentally, because of technological difficulties, it was
laser-based spectroscopic methods. The CMB method, intro-
not until the 1960s and 1970s that the field received a great
duced in the 1950s" and widely applied in the 1960s to reac-
impulse with the work of Polanyi and co-workers on IR che-
tions of alkali metals using the hot-wire surface-ionization
milumine~cence,~~~ the work of Parker and Pimentel on
detector (the 'alkali era'),4*10-13reached its maturity in the
chemical lasers,' and that of Herschbach?," Lee and co-
1970s with the development of universal machines,16 which,
workers3*' and others,I2 on molecular beams. This early
using a mass spectrometer as a detector, rendered the method
experimental work was mostly devoted to atom-diatom reac-
generally applicable. The technique attained high levels of
tions and is well documented in many reviews13 and in
sophistication in the 198Os, which was well expressed by the
Levine and Bernstein's book.'
study of the F + H,(D,) reaction by Lee and co-worker~.'~
The progress that has been achieved over the years has
The CMB method allows the direct observation of the conse-
been due to a very stimulating and fruitful encounter between
quences of single reactive collisions of well controlled
reagents.18 In a CMB experiment the internal states and the
t Permanent address : Dipartimento di Chimica, Universitri di velocities of the reactants can be selected, usually by super-
Roma 'La Sapienza' 00100, Roma, Italy. sonic expansion and seeding techniques, the initial relative

576
velocity vector is well defined in magnitude and direction;
hence, the measured quantities of scattered products can be
related to the mechanics of single collisions. The experimental
observables which provide information on the reaction
dynamics are the angular and velocity distribution (i.e. the
doubly differential cross-section) of reaction products. The
state-to-state differential cross-section (DCS) for a chemical
reaction is the quantity most easily related to classical and
quantum-mechanical models based on collision theory.
Although most of the measured DCS in CMB experiments
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are averaged over initial impact parameters (unavoidably)
and final internal quantum state distributions, in favourable
cases product-vibrational resolution has been achieved.'
Note that, while measurements of the energy distribution of
product molecules is not a unique capability of the CMB
method, it can actually be better derived by laser spectro-
scopic techniques (see below) or from chemilurninescen~e~~' desire to overcome the main difficulty encountered in the
and chemical laserg studies when applicable; information on
product angular distributions of bimolecular reactions is
obtainable directly from CMB experiment^.^^'^ (While this
capability was a prerogative of the method until very recent-
ly, nowadays DCS data can also be derived from experiments
performed in-bulb employing only laser techniques ; see
below). This is quite important, since the product angular dis-
tribution contains direct detailed information on the mecha-
nism and dynamics of the reactive event and, hence, it
provides a physical observable which is very sensitive to the
nature of the reaction PES, enabling us to learn about the
forces that control chemical reactivity.
Laser-based spectroscopic methods were introduced in the
field of reaction dynamics in the 1970s by Zare and co-
w o r k e r ~and , ~ ~became widespread in the 1980s following the the PES for a chemical reaction is the technique developed
development and sophistication of laser sources and modern
spectroscopic techniques. Application of various linear and
non-linear laser techniques, such as LIF (laser-induced
A u o r e s ~ e n c e ) , ~REMPI
~ ~ ~ ' (resonant-enhanced multiphoton diate.
ionization)2',22 and CARS (coherent antistokes Raman
spectro~copy),~~ within time-resolved pump-probe schemes,
have provided detailed information on the quantum
(rovibrational) states of nascent reaction products. Among
the spectroscopic techniques special mention goes to the IR
chemiluminescence method developed by Polanyi and co-
worker~.~*' In these experiments the collision-free regime is full understanding of the PES for reaction. For more complex
usually attained using low-pressure conditions.
The combination of molecular beams and lasers permits, in
principle, the most detailed investigation of the dynamics of a
chemical reaction, since this combination allows us to investi-
gate gas-phase reactions occurring at well defined collision
energies, with reactants in selected quantum states and with
nascent products probed in their individual quantum states.
Unfortunately, the difficulties are such that only a few mea-
surements of product state-resolved DCSs have been made to
date. In particular, reactive DCSs resolved in both vibra-
tional and rotational states of the product (the ultimate goal
in reaction dynamics) have been reported only for the reac-
tion H + Dz(v = 0, j = 0)-+ HD(v', j') + D by Welge and co-
w o r k e r ~ , ~using the novel Rydberg-atom time-of-flight
spectroscopy method. Coupling of lasers and crossed pulsed
beams is especially promising and is expected to play an
important role in the study of reaction dynamics; state-
selected DCSs can be derived in favourable cases by LIF or
REMPI detection of the products at the collision centre
exploiting Doppler profile^^^,^^ or ion-imaging tech-
n i q u e ~ . ~ Recent
~ . ~ ' sophisticated experiments by Liu and co- ment of chemical reaction dynamics because of their acces-
w o r k e r ~ employing
~~ two crossed pulsed beams with
specified internal states and relative velocities have shown
that the crossed beam technique with LIF or REMPI
probing at the coIlision centre, also gives the means for
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J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
studying chemical kinetics at a state-specific level: rate con-
stants as a function of temperature are deduced from mea-
surements of the translational energy dependence of
state-specific reaction cross-sections. Although the imaging
technique in crossed pulsed beam experiments has been
applied so far only to the H + D, reaction by Chandler and
c o - ~ o r k e r swith
~ ~ REMPI detection of the D atom product,
it holds promise for other reactions and for state-specific
detection of the molecular products as well. A recent alterna-
tive approach for deriving reactive DCS abandons the most
intuitive crossed beams method and exploits, essentially, only
laser techniques; state-to-state DCS can be deduced from
photoinitiated reactions in a pulsed beam3' and also in
bulb,3' using velocity-aligned atomic reagents produced by
laser photolysis and sub-Doppler product detection. The
development of this technique has been prompted by the
coupling of crossed beams and laser methods to probe pro-
ducts state-specifically, namely the very low product number
densities which give very low signal levels. On the time-
domain side, femtosecond laser techniques allow the course
of a chemical reaction to be followed in real-time, so that the
fundamental question 'How does the system evolve from
reactants to products?' can be challenged. In these experi-
ments the zero time of the reaction is triggered by photolysis
of a suitable precursor of the atomic (or radical) reactant
starting from van der Waals impacted reagent^.^'-^^ These
real-time techniques, pioneered by Zewail and co-workers,
3 2 + 3 3 allow spectroscopic investigation of both the final pro-
ducts and the transition state. In this regard, another novel
approach for directly exploring the transition-state region of
by Neumark and co-workers3' measuring the photoelectron
energy spectrum following electron photodetachment of an
appropriate precursor negative ion of the reaction interme-
The experimental progress was also accompanied by a for-
midable advance in theoretical m e t h o d o l o g i e ~ and~ ~ *com-
~~
puter c a p a b i l i t i e ~during
~ ~ the last decade, so that for simple
(three-atom) systems state-to-state DCS can be compared
with exact quantum-mechanical dynamic calculations on ab
initio or semiempirical PESs and, ultimately, this leads to a
systems (four, five or more atoms), dynamic experiments are
harder to do, but still they are desirable considering that the
quantum reactive scattering theory is currently challenging
the development of accurate, and yet practical, computa-
tional methodologies to tackle chemical reactions beyond
A 3- BC.39-59
In this Faraday Research Article we survey recent work
carried out in Perugia on reactive scattering studies of atom-
molecule (three-atom) and radical-molecule (four-atom) ele-
mentary gas-phase chemical reactions using the CMB
technique with universal mass-spectrometric detection. The
work described, which witnesses some of the current capabil-
ities of the CMB technique, is put in the context of the recent
theoretical developments.
After this general introduction, and in order to introduce
the different topics considered here, a more specific summary
of the present status of theory and experiment in reaction
dynamics is useful.
The reactions H + H, and F + H2 (and their isotopic
variants) have been the benchmark systems in the develop-
sibility to both detailed and
experimental s t ~ d y . ~ ~ PESs ~ ~ 'of ~chemical
~ ~ ~ accu-
* ~ ~ ~ ~ ~ *
racy (i.e.within 1 kJ mol-l) have been calculated for the sim-
plest reaction, H + H2,64and, very recently, almost compar-

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
able accuracy has been achieved for the reaction F H2.60 +
Less accurate PESs, both semiempirical and ab initio, are
available for a variety of other A + BC systems and also for
some AB + C D reactions. During the last few years, follow-
ing an impressive progress in quantum reactive scattering
methods and computer capabilities, fully converged three-
dimensional (3D) quantum scattering calculations of state-to-
state differential cross-sections have been performed for the
H + H, and F + H, reactions and accurate comparisons
with very detailed experimental observables carried
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O U ~ . ~ ~ * To ~ date,
~ - ~the ~ exact
* ~ ~3D* quantum
~ ~ scattering
calculations of state-to-state DCS on a reliable ab initio PES
have only been carried out for one other neutral three-atom
system, namely, for the prototypical reaction C1 + H, .65
However, in contrast to H + H, and F + H, , no experimen-
tal dynamical information is available for Cl + H,. There-
fore, we have recently carried out, for the first time, CMB
experiments on C1+ H, and C1 + D, with product vibra-
tional resolution. Some of the preliminary results will be dis-
cussed below.
The progress made in the solution of the reactive scattering
problem involving three-atoms on a single adiabatic PES is
such that the four-atom problem can now be attempted,
which is the natural extension of A + BC towards more
complex systems. Indeed, the theoretical dynamicists have
already started to focus their attention on diatom-diatom
system^.^'-^' The quasiclassical trajectory method for treat-
ing the dynamics of four-atom reactions has been implement-
ed and, very recently, Schatz and c o - w o r k e r ~ ~ ~have -~'
+
applied it to the OH + CO and O H H, reactions. During
these last few years the quantum scattering theory has also
been extended to four-atom reactions and calculations
(although with some degree of approximation) of rate con-
stants, and state-selected integral and differential cross-
sections have been r e p ~ r t e d . ~ ' - ~Very ~ recently,
full-dimensional (6D) quantum-mechanical calculations of the
rate constant as a function of temperature4' and accurate
quantum computations in six-dimensional space of reaction
probabilities, initial state-selected reaction cross-sections and
rate ons st ants^^-^^ for the benchmark OH + H, reaction,
have been carried out. Exact quantum scattering calculations
of state-to-state DCS for this prototypical four-atom reaction
may very soon be within the reach of modern computer capa-
bilities. These theoretical developments have come out at a
propitious time because of the new experimental studies on
the dynamics of four-atom r e a ~ t i o n s . ~ ~Four-atom
* ~ ~ , ~ ~ - ~particular,
diatom-diatom reactions are actually radical reactions. They
are, in general, known to play a paramount role in many
practical systems, from combustion to atmospheric chemistry,
from plasma to interstellar chemistry. The two reactions
which have taken a leading role in this area, namely
OH + H, and OH + CO, are appropriate examples of prac-
tical interest too.83*84The kinetic^"*^^-'^ of these two reac-
tions and the dynamics32~34*66-82 of the reverse processes
have been investigated very extensively, but surprisingly no
information has been available on the dynamics of the direct
processes until lately. By exploiting the capability to generate
continuous supersonic beams of OH radicals, measuremeni
of reactive DCS by the CMB method for these two important
radical-molecule reactions have been very recently reported
from our lab~ratory.~'*~' This extends, beyond the A + BC
case, the possibility of detailed comparison with the results of
quasiclassical and quantum-mechanical dynamical calcu-
lations on ab initio PESs and is the second topic to be con-
sidered below. Note that, prior to the present studies,
investigation of free-radical reactions with continuous
crossed beams and mass-spectrometric detection remained
limited to the pioneering work of Ross and co-workersg4
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577
with effusive beams of CH, and OH radicals, and, more
recently, to a study in Grice's groupg6 and a study in Lee's
groupg7 using supersonic CH, beams. Recently, nascent
product internal state distributions of several free-radical
reactions have been determined using pumpprobe laser
methods and in crossed pulsed beam experiments with laser
detection;,Ob no DCSs were measured.
An interesting problem in reaction dynamics is the role of
the excitation of the internal degrees of freedom of the
reagents. Most dynamical studies to date have dealt with
reactions of the type atom +diatom occurring on the
ground-state PES; for many of these reactions the role of
vibrational and rotational excitation has been examined both
at the experimental and theoretical levels.'-2 Much less is
known about the role of electronic excitation on reaction
dynamics. Among the various forms of internal degrees of
freedom and their effect on chemical reactivity and dynamics,
the electronic one is quite peculiar, since the extent of elec-
tronic excitation is such as to drive even reactions which are
strongly endoergic for the ground-state species. The role of
electronic excitation is actually that of driving the reaction on
a PES different from the ground state PES and, in general, it
is the different topology of the excited PESs which deter-
mines the different reactivity of the various electronic states.
Whilst the kinetics of electronically excited atoms have been
, ~ ~ during the last 10 years have
investigated e x t e n ~ i v e l yonly
their reaction dynamics started to be examined using
LIF99-105 and IR chemiluminescence (IC)106-'08 in low-
pressure cells, LIF in crossed beams,"' LIF in laser-initiated
half-reactions within a pulsed beam,'" and also by IR
absorption.' '' More recently, the use of crossed beams com-
bined with laser excitation has made it possible to study the
reaction dynamics of different electronic states of an atom
(alkali or alkaline-earth metal) as a function of collision
energy and alignment of the excited orbital under well
defined conditions.' l 2 An atomic species whose excited states
are of great interest from both fundamental and practical
points of view is oxygen, a non-metal atom with the well
known peculiar chemical behaviour. Early kinetic and
dynamic studies showed that the first electronically excited
state O('D) is much more reactive than the ground state
O(3P).108,113-1 15 w ith the development of continuous super-
sonic beams of O('D) it has become possible to measure
product angular and velocity distributions from reactions of
this important species in CMB experiments' 1611 l 7 and, in
~ by using continuous supersonic beams containing
both O(3P) and O('D), it has become possible to explore
directly, under the same experimental conditions, the effect of
electronic excitation on the reaction dynamics of atomic
oxygen.'18 This will be illustrated here using the reaction
O(,P,'D) + H,S.
Before the results are introduced, the experimental tech-
nique used to obtain them will be described.
2. Experimental Method
2.1 Principles and Outcome
In a typical CMB experiment, beams of atoms and molecules
with narrow angular and velocity spread are crossed in a
vacuum chamber and the angular and velocity distributions
of the products are recorded after a single and well defined
collisional event using a rotatable electron-impact ionization
mass spectrometer detector. This type of detector is capable
of detecting arbitrary fragments resulting from chemical reac-
tions, i.e. it is universal, and this is the key which has been
central to the advancement of molecular beam reaction
dynamics. The measurements are carried out in the labor-
atory (lab) frame of coordinates, while for the physical inter-
pretation of the scattering process it is necessary to transform

578
the data [angular, N(O), and velocity, N ( 0 , u) distributions]
in a coordinate system which moves with the centre-of-mass
(c.m.) of the colliding system.' This transformation is fairly
straightforward and the relation between lab and c.m. fluxes
is given by :
(where 0 and u are lab angle and velocity, respectively, and 8
and u are the corresponding c.m. quantities), i.e. the scat-
tering intensity observed in the laboratory is distorted by the
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transformation Jacobian u2/u2from that in the c.m. system. A
velocity vector (so called 'Newton') diagram shown in Fig. 1
illustrates the nature of the 1ab-c.m. transformation for an
'A + BC' The vector of the c.m. velocity, u,.,. ,
pointing in the direction of the c.m., determined by partition-
ing the initial relative velocity vector u, according to conser-
vation of linear momentum, allows one to relate the lab
velocity trAB and scattering angle 0 to the c.m. velocity uAB
and angle 8 through the vector addition vAB = vc.m. + uAB.
Since the electron-impact ionization mass-spectrometric
detector measures the number density of products, N(@), not
their flux, the actual relation between the lab density and the
c.m. flux is given by:
Because of the finite resolution of experimental conditions,
i.e. finite angular and velocity spread of the reactant beams
and angular resolution of the detector, the 1ab-c.m. trans-
formation is not single-valued and, therefore, analysis of the
laboratory data is usually carried out by forward convolution
procedures over the experimental conditions of trial c.m. dis-
tributions (i.e. c.m. angular and velocity distributions are
assumed, averaged and transformed to the lab for compari-
son with the data). When the initial velocity distributions (of
the reagents) are quite narrow, this procedure allows one to
recover the c.m. distributions with reliability.3*4*18 The final
outcome of a reactive scattering experiment is the generation
of velocity flux contour maps of the reaction products, i.e. the
plot of intensity as a function of angle and velocity in the c.m.
system, Ic.m.(8, u). This contour map can be regarded as an
image of the reaction.
2.2 Crossed Molecular Beam Apparatus
The CMB apparatus used in our laboratory follows the clas-
sical design of Lee et U E . , ' ~ where the entire detector assembly
is rotating with respect to the fixed beam sources. The appar-
VAB R pumped; however, in some cases, as for the OH and C1
Fig. 1 Velocity vector (or 'Newton') diagram showing the relation-
ship between laboratory and centre-of-mass velocity vectors and
+
angles for the reaction A BC -+ AB + C (see text)
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J, CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
atus is the same as previously used for measuring elastic and
total (elastic + inelastic) differential cross-sections for atom-
atom and atom-molecule collisions to derive intermolecular
potentials,'20 and has recently"' been optimized for reactive
scattering experiments. Fig. 2 shows a cross-sectional top
view of the apparatus. Briefly, two well collimated supersonic
beams of reagents are crossed at 90" in a large scattering
chamber with background pressure in the mbar range,
which assures the single collision conditions. A mass spec-
trometer, contained in an ultra-high-vacuum (UHV)
chamber, serves as detector of the reaction products. The
mass spectrometer can be rotated in the collision plane
around an axis passing through the collision centre and the
velocities of the particle can be derived from time-of-flight
(TOF) measurements using a pseudo-random chopping disk.
In the present experiments a selection of the velocities, as well
as internal quantum states, of the reactants by supersonic
expansion, is achieved. The selection of the translational
energy of the products also gives (by energy conservation)
their internal (rotational + vibrational + electronic) energy.
Since the apparatus has been described previously, only its
essential features are reported here. The main scattering
chamber is a welded aluminium alloy box with internal
dimensions 110 cm x 110 cm x 57 cm, with a rotatable lid,
supported by a 76.2 cm id ball bearing, which carries the
detector unit and its pumping system. The main chamber is
pumped by a large two-stage (77 and 14 K) cryo-pump and
two baffled diffusion pumps for a total pumping speed of
about 11OOO 1 s-'. This set-up allows US to keep a clean
vacuum in the main chamber down to 3 x mbar under
operating conditions. The detector unit is made of 304L
stainless steel and consists of three different pumping stages
in three nested UHV chambers. In its present configuration
the first region is pumped by a 400 1 s-' magnetically sus-
pended turbomolecular pump, the second region by a 170 1
s-' turbo-pump and a 220 1 s-' ion-pump, while the inner-
most region is pumped by an 80 1 s-' ion-pump, a 320 1 s-'
magnetically suspended turbo-pump and a 400 1 s - I two-
stage (77 and 13 K) cryo-pump. In addition, both the second
and third regions are liquid-nitrogen cooled. The detection
system consists of an electron-bombardment ionizer, a quad-
rupole mass filter and an off-axis (90") secondary electron
multiplier. The ionizer is located in the innermost (third)
'
region of the detector maintained in the 10- mbar pressure
range.
The beam sources are placed in separately pumped side
chambers, made of stainless steel, which insert into ports in
the main chamber. Usually, each source is differentially
experiments, the secondary molecular beam source was
brought close to the collision region, without differential
pumping, to gain intensity. The source chambers and all the
beam-defining elements are readily interchangeable. The
beam sources are pumped by unbamed 6000 1 s - l diffusion
pumps backed by 500 m3 h-' roots pumps, while the differ-
ential regions are equipped with 2400 1 s - l diffusion pumps
and 20 m3 h-' rotary pumps.
Supersonic molecular beams of hydrides species (such as
H,S) are obtained by expanding pure gases through a heat-
able stainless-steel nozzle (0.1 pm diameter) to prevent signifi-
cant cluster formation. Typical pressures range from 0.3 to
1.0 bar while angular and velocity divergences are 2.9" and
about 20%, respectively. The hydrides are expected to be in
the ground electronic and vibrational state and, because of
the rotational cooling during the supersonic expansion they
are in the lowest few rotational levels.
Supersonic molecular beams of H,, D, and CO are instead
generated by expanding pure gases at a stagnation pressure

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
KI
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Fig. 2 Top view (cross-sectional)of the crossed molecular beam apparatus, showing the scattering chamber, the doubly differentially pumped
beam sources, the triply differentially pumped electron-impactquadrupole mass spectrometer detector and the time-of-flight chopper
of 3-5 bar through a 75-100 pm diameter stainless-steel
nozzle, kept at about 350-600°C to increase the beam trans-
lational energy. With only one stage of differential pumping
the angular divergence is about 5" and typical FWHM veloc-
ity spreads are 15%. The H,, D,, and CO molecules in the
beams are estimated to be in the lowest few (j= 0, 1, 2) rota-
tional levels of the vibrational and electronic ground state.
2.3 Supersonic-beam Source of Atoms and Radicals
In reactive scattering experiments use of supersonic beams of
stable species is straightforward, but use of suitable beams of
unstable species, such as non-metal atoms and radicals, pre-
sents some difliculties. In an apparatus equipped with a con-
tinuous wave (cw) detector, such as a mass spectrometer, the
optimum source of atom and radical beams should also be
continuous. Therefore, photolytic methods are usually ruled
out, since they are limited by the very poor duty cycle of the
intense UV pulsed lasers required for photodissociating a
suitable precursor. The above consideration leaves essentially
two ways of generating a cw beam of radicals: pyrolysis and
electrical discharge. While the thermal method has been
shown to work very well for producing intense supersonic
beams of C1 atoms,122 it is not very suitable for generating
intense cw beams of oxygen atoms or hydroxyl radicals,
although an example of thermal generation of effusive beams
of these two species exists.'23 Of the possible electrodeless
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579
scattering chamber
discharges, the radio frequency (RF) was found to be superior
over microwave (MW) discharges. Sibener et ~ 1 . ' ' ~have
shown that an RF discharge can operate at higher pressures
and plasma temperatures than a MW discharge,lz4 so
producing supersonic beams of oxygen atoms with lower
velocity spread, while giving a much higher degree of molecu-
lar dissociation, and permitting the achievement of higher
translational energies. Moreover, it was demonstrated that
from a high-pressure RF discharge beam source O('D) atoms
(lifetime z x 150 s) can also be produced when dilute mix-
tures of 0, in He are used,' l 6 and this has opened the way to
the investigation of O('D) reactions in crossed beams.' l 7
For the above reasons we have chosen the RF discharge
method for our experiments. A detailed description of our RF
discharge beam 'source, which is based on the design of
Sibener et uL116 and has been optimized for O('D) gener-
ation, has been given recently.12' Briefly, high levels (up to
330 W) of RF power are fed through a parallel LC circuit
(resonance frequency x 14 MHz) into a plasma contained in
a water-cooled quartz nozzle with typical orifice diameter of
250 pm. The plasma is directly localized behind the orifice of
the nozzle, which permits a very high degree of dissociation
(up to 95% with 5 2 0 % 0,-Ne gas mixtures, up to 83% with
5% 0,-He mixtures, and almost 100% with 2.5% Cl,-Zle
mixtures at typical total pressures of 250-400 mbar) and in
the case of 0,-He 0,-Ne mixtures also significant concen-
trations of electronically excited 'D oxygen atoms. The ratio
of O('D) to O(3P) atom concentrations is estimated to be

580
quite small (a few percent), but it is not found to vary signifi-
cantly passing from 5% 0,-He to 5% 0,-Ne gas mixtures,
when operating at 350 mbar and 260 W and using a 250 pm
nozzle orifice. Thus, by simply changing the gas mixture,
supersonic beams of O(3P,'D) atoms with translational
energy varying over a wide range (0.18-0.8 eV) become avail-
able. While the presence of O('D) in the beam may be a com-
plication in the study of O(3P) reactions, it also offers the
exciting possibility of studying those of O('D). When the cor-
responding O(3P)reaction is endoergic or has a much smaller
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cross-section (which is actually typical), it is possible to study
only the O('D) reaction: this is the case of the hydrogen dis-
placement reactions of O('D) with hydrogen halides, recently
studied in our l a b o r a t ~ r y . ' ~ ~In* ~other ~ ~ *cases,
' ~ ~ where
triplet and singlet reaction channels are both exoergic, the
simultaneous presence of O(3P) and O('D) in the beam can
permit a direct comparison between the reaction dynamics of
the two different species under the same experimental condi-
tions, provided the two contributions can be disentangled in
the measurements: this is the case illustrated in Section 5
with regard to the O(3P,1D)+ H,S reactions.
Recently, intense supersonic beams of OH radicals have
been generated by using the same RF discharge beam source
starting from dilute (2.5%) mixtures of H,O in He or He-Ne
The carrier gas is bubbled in water at 4°C to main-
tain a total pressure of 250-300 mbar. Peak velocities above
3000 m s-' and velocity spreads of about 20% are attained
with H,O-He mixtures at 300 W. The OH radicals in the
beam are expected to be in the lowest 211electronic state,
since possible electronically excited OH will radiatively
cascade to the ground state in 4 1 J A S . ' ~The ~ OH beam is
also expected to be rotationally cold, since rotational relax-
ation of OH by H,O is known to be almost gas kinetic
( k = 2.2 x lo-'' cm3 molecule-' s-').I2' Vibrational relax-
ation of OH by H,O is known to be also rather fast
[ k = (1.3-2.6) x lo-" cm3 molecule-' s - ' ] ' ~ ~ and by H
and 0 atoms even faster (of the order of lo-'' cm3
'
molecule- s - ' ) . ' ~ ' Although we have some indication from
our scattering results that O H in the beam is predominantly
in the u = 0 level, a detailed characterization of its internal
quantum states is desirable. Other species produced in the
discharge, such as atomic and molecular oxygen and hydro-
gen, do not interfere in the reactions studied so far and dis-
cussed in the following.
Very recently, we have also generated intense supersonic
beams of C1 atoms by using the same discharge beam source.
Although this is the first time, to our knowledge, that a RF
discharge is used for this purpose, we note that a microwave
discharge source has been used successfully for a number of
years by Grice and c o - w o r k e r ~ ' ~ ~ -to
' ~ generate
' supersonic
beams of Cl atoms for CMB reaction dynamics studies.
Again, the RF discharge method gives higher C1 beam inten-
sities and speed ratios than the MW discharge method, as
already noted for oxygen atom beams. A typical velocity
spread for C1 beams produced by RF discharge of 150 mbar
of a 2.5% C1,-He mixture through a 250 pm quartz nozzle is
better than 25%. While RF discharges of C1,-He mixtures
are characterized by quite a high plasma temperature (up to
2000 K) which may lead to nozzle enlargement at high RF
power, discharges in C1,-0,-He are much colder (ca. 1200
K) and produce very stable beams even at high pressure
(300-400 mbar). By using these discharge conditions, super-
sonic beams of C1 atoms, and of C10 radicals, with velocity
spread better than 20% have been generated.13, For com-
pleteness, we recall that intense supersonic beams of C1 atoms
have been more traditionally generated by thermal disso-
ciation of C1,-rare-gas mixtures in a graphite oven. Over
many years Lee and c o - ~ o r k e r s , ' ~ ~have * ' ~ ~used this
View Article Online
J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
method? to investigate the dynamics of several C1 reactions,
including Cl + 0, .134
2.4 Angular and Velocity Distribution Measurements
During a reactive scattering experiment the reactant beam
velocities are measured by single-shot TOF analysis to better
than 1%, using a high-speed multichannel scaler and a
computer-controlled CAMAC data acquisition system.12'
Product velocity distributions, N(O, a), are obtained at selec-
ted lab angles using the cross-correlation TOF techniq~e'~'
with four 127-bit pseudorandom sequences. The ffight length
is 23.6 cm (24.5 cm in the most recent arrangement). Typical
counting times vary from 10 to 100 min, depending on the
signal and background levels. High time resolution is
achieved by spinning the TOF disk, located at the entrance of
the detector (see Fig. 2), at 393.7 Hz corresponding to a
shutter function and dwell time per channel of 5 ps.
The angular dependence of the reactive differential cross-
section is measured by rotating the detector unit in the plane
defined by the two beams. The lab angular range accessible
to the measurements is about 145" and the angular resolution
is set to 1". The lab angular distributions of products, A!(@),
are obtained by taking several scans of, typically, 30-200 s
counts at each angle. The secondary target beam (in the
present experiments the beam of stable molecular species) is
modulated at 160 Hz by a tuning fork chopper. The back-
ground and signal plus background counts are obtained from
a pulse counting dual scaler synchronously gated to the
tuning fork.
3. Three-atorn Reactions: C1+ D2
In the series of the halogen-hydrogen reactions, which have
played a central role in fundamental chemical kinetics since
the beginning of the century, the systems F + H, and C1
+ H, have received the most attention at the kinetic level,
. ' ~ ~ F + H,
both experimentally and t h e ~ r e t i c a l l y . ' ~ ~While
has also been investigated in very great detail from the
dynamics 7*35*37*60*61 for C1 + H, only theo-
retical has been reported on the dynamics,
with experimental studies completely lacking.
The PES of F + H, has been calculated ab initio with
almost chemical accuracy6' and although similar calculations
have also been carried out for C1 + H,, the accuracy seems
to be lower because of the larger number of electron^.'^'
Semiempirical methods have been widely used for both F
+ H, and C1 + H, P E S S . ' ~ ~Dynamical
?'~~ studies by quasi-
classical and quantum-mechanical techniques have been per-
formed on F + H, and C1+ H, as well as reverse and
exchange r e a ~ f i o n s . ~ ~ ~In
' ~ particular,
~-'~' for both systems,
exact 3D, fully converged, quantum scattering calculations of
state-to-state DCS have been carried out on semiempirical
and ab initio PESs.36,37*60-62*6s While F + H, has been
investigated very extensively at the dynamical level with a
variety of experimental 7935 which has led to
detailed comparisons 369 7*60-6 between experiment and
theory and contributed enormously to our understanding of
chemical reaction dynamics, for different reasons the homolo-
gous C1 + H, system could not be studied. F + H, is strong-
? The first CMB investigation of a C1 atom was reported by
Herschbach and co-workers in 1968 using an effusive, thermally gen-
erated, C1 atom beam.'33
 View Article Online

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91 58 1

for F + H, (k298 = 2.5 x lo-'' cm3

r molecule-' s - ' ) ' ~ than
~
molecule- ' s- 1).136 Consequently, application of the CMB

40 t -
-
-
-
-
10

EE5
a

2 [CI- - - D- - - D]*
5 20-
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-Cl(v= I) + D
D
technique, which has been so successful for F + H, and iso-
topic variant^,'^ has been hampered in the case of C1+ H,
because of the more unfavourable kinematics of this system,
in which the heavy HCl product is constrained to be confined
- J very near the C1 beam and within a very small Newton
- sphere (see below and Fig. 4). Nevertheless, we have been able
- 15
- to overcome such difficulties and provide detailed dynamical
results for the important C1 + H, system to be compared

Q,
c
Q, with those of theoretical calculations. Here we present pre-
-
liminary data on the reaction:
10 - C1+ D, -+ DCl + D; AH: = 6.86 kJ mol-'

D Cl(v= 0) + D at a collision energy of 26.8 kJ mol-', that is, slightly above

0 was necessary to go to a high angular resolution set-up of the
CI + D ~ ( V 0)
=
Fig. 3 Energy level and correlation diagram for the C1 + D, reac-
tion, with the rovibrational levels of the product indicated. The
arrow indicates the experimental collision energy
ly exoergic (AH" = -134.3 kJ mol-') allowing the H F
product to be formed up to 0' = 3 in the thermal energy
range, while C1 + H, is nearly thermoneutral (AH" = 4.3 kJ
mol-') and the HCl (DCl) product can only be formed in the
ground vibrational level for energies up to 40 (32) kJ mol-'
(see Fig. 3, where the energy level and correlation diagram for
C1 + D2 is depicted). These features ruled out the IR-
chemiluminescence method for investigating this reaction.
Moreover, while F + H, has a barrier of about 6 kJ mol-1,60
that of C1 + H, is significantly larger (about 25 kJ mol-I),
141~143so that the rate at room temperature for the reaction
C1 + H, is considerably slower (k298 = 1.8 x cm3
the barrier to reaction. For the success of the experiment it
apparatus, which allowed us to explore in detail the narrow
laboratory angular range, close to the Cl beam (down to
0 = 4"), in which the DCl product is confined to be scat-
tered. On the left-hand side of Fig. 4 we show the angular
distribution of the DCl product (detected at m/z = 39) from
the C1 + D, reaction at a collision energy of 26.8 kJ mol-',
together with the most probable Newton diagram. Note that
the product is almost completely confined to the right of the
c.m. angle in the lab frame, that is in the backward direction
with respect to the C1 beam, and it is sharply peaked at an
angle nearly tangent to the maximum Newton circle, within
which the product is confined to be scattered on the basis of
energy and linear momentum conservation. These two fea-
tures immediately suggest that the mechanism of the reaction
is direct (of the rebound type) and that a very large fraction
of the total available energy is disposed into translation of
the products. Velocity spectra at three selected angles have

1.0- mol-'
n '
rn
.-
c
C
3

4
J 0.5 -
\
c*

0
v
z
0.0 I
0 f 10 20 30
J I : @,,,/degrees
.' J

-
I

I
+
I .

1000 m s-'

"Cl
1000 rn s-'

Fig. 4 (a) DCl product laboratory angular distribution from the CI + D, reaction at E, = 26.8 kJ mol-'. The solid line represents the angular
distribution calculated with best-fit c.m. translational energy and angular distributions.The circle in the Newton diagram delimits the maximum
DCl speed assuming that all the available energy goes into translation. (b) DCl product centre-of-mass flux (velocity-angle) contour map with
3D perspective.

582
also been recorded. From the angular and velocity distribu-
tion data in the lab frame preliminary c.m. best-fit angular
and translational energy distributions have been derived;
they are shown in the 2D and 3D product flux contour map
representation on the right-hand side of Fig. 4. The c.m.
angular distribution is almost completely confined in the
backward hemisphere and peaks at 6 = 180". This suggests
that the favoured orientation for reaction is collinear. About
80% of the total available energy is deposited into translation
and reflects strong repulsive forces between DCl and D, after
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that the saddle point is passed. The exceptionally high trans-
lational excitation of the products can be well appreciated in
the contour map of Fig. 4, which shows the DCl product to
be confined almost at the limit (dashed circle) of energy con-
servation. Since at this collision energy the DCl product can
energetically be formed only in U' = 0, energy conservation
also gives us, by difference, the amount of energy released
into rotation (about 20%). Collisions with impact parameters
larger than zero are those which lead to product rotational
excitation. It appears that the dynamics of C1 + D, resembles
+
that of H D, (and D + H,), suggesting similarities of the
PES topol~gies.'"~
In experiments at higher E , ( z 38-42 kJ mol-') on the
+
C1 D, reaction, also formation of DCl (u' = 1) has been
observed and resolved in angular distribution measure-
m e n t ~ . 'The~ ~ lab angular distribution of HCl from the C1
+ H, reaction at E , = 23.8 kJ mol-' has also been mea-
It shows the same features of the DC1 distribution,
i.e. it is strongly back-scattered.
Ab initio ~ a l c u l a t i o n s 'of~ ~the PES indicate that collinear
approach of C1+ H, is the dominant geometry leading to
chemical reaction, in agreement with the experiments. Fewer
dynamical computations are available on the reaction C1
+ H, compared to the reaction F + H,. Much of the theo-
retical work was carried out by using a semiempirical LEPS
PES. Transition-state theory, collinear (1D) quantum-
mechanical and classical calculations as well as 3D trajectory
computations were performed.' 38- 140 The LEPS surface
(termed SPK)143 with a classical barrier height of
'
32.2 kJ mol- (measured from the potential minimum in the
entrance channel) was recently improved in the H-Cl-H
conformation by large-scale ab initio calculations.14' The
new surface (termed CSPK)14' maintains the same barrier
height (the adiabatic barrier is 23.4 kJ mol-' ) and collinear
transition-state geometry. Persky' 39 has carried out a
detailed classical trajectory study on the SPK surface for the
C1 + H,, D, and H D systems. Reaction probabilities, cross-
sections, rate constants, activation energies, product energy
partitioning and angular distributions were computed for the
initial vibrational state u = 0 and rotational states j = 0-4 of
H2 (D,) and collision energies in the range between threshold
( a 20 kJ mol-l) and 50 kJ mol-l. The trajectory results for
the kinetic isotopic effects and for the absolute values of the
rate constant were found to be in very good agreement with
the experiment. A preliminary comparison between the mea-
sured and calculated angular distributions for C1 D, shows +
a good qualitative agreement.
Recently, Launay and Padkjaer6' have performed exact
quantum calculations of cross-sections for Cl + H, using the
hyperspherical method from threshold up to about 70 kJ
mol-' using the CSPK surface. In addition to state-to-state
integral cross-sections, they also calculated state-to-state
DCS at E , = 22.2, 46.4 and 70.7 kJ mol-'. At E , = 22.2 kJ
mol- the c.m. angular distribution calculated for the reac-
tion Cl + H,(u = 0, j = 0) -+ HCl(u' = 0, j ' ) + H is confined
completely in the backward hemisphere and peaks at
6 = 180", in line with the present experimental results at
slightly higher E , . The calculated fraction of energy in rota-
View Article Online
J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
tion is about 8%. Calculations at higher E, indicate that the
c.m. angular distribution also starts to protrude in the
forward hemisphere and the fraction of energy in rotation
increases as E, is increased. The trends observed in trajectory
cal~ulations'~ appear
~ to be confirmed by the quantum
results.65 It is, of course, desirable to have experiments at
different E, and dynamical calculations at the same E, of the
experiment for both C1+ H, and C1+ D,, in which the
internal rotational distribution of the H, (D,) reactant beam
is taken into account. These calculations, on a new ab initio
surface,14' are in progress in Truhlar's using exact
quantum methods and in Aoiz's groups'"' using the QCT
method and will permit a detailed comparison between
experiment and theory in the near future.
4. Four-atom Reactions: OH + H, and OH + CO
The four-atom reactions:
OH + H, -+ H,O + H; AH: = -61.9 kJ mol-' (1)
and
OH + CO -+ CO, + H; AH: = - 102.5 kJ mol-' (2)
have recently emerged as benchmarks for theoretical studies
of systems involving four atoms. In particular, the reaction
OH + H,, comprising three hydrogen atoms and an atom of
the first row of the periodic table, is expected to play for the
four-atom case the same role played by H + H, and F + H,
for the three-atoms. In fact, the system is amenable to high-
quality ab initio calculations of the PES and is the first four-
atom candidate for exact quantum-mechanical state-to-state
scattering calculations. Although the reaction OH + CO rep-
+
resents a more challenging task than OH H, for theory,
because of the heavier atoms, it is nevertheless taking the
prototype role of a complex-forming reaction involving four-
atoms with a deep potential well between reactants and pro-
ducts. Large scale ab initio electronic structure calculations of
''
the PES148-1 and quasiclassical and (approximate) quan-
tum scattering calculations of the dynarni~s~'-'~~~~~*'~~*''~
have recently been reported both for OH + H, and
OH + CO. In Fig. 5 the energy level and correlation dia-
grams for the two reactions are shown comparatively.
Besides their fundamental interest, reactions (1) and (2) are
also of great practical relevance. This importance stems from
the fact that the hydroxyl radical is a key species in atmo-
spheric chemistryE4as well as in c o m b ~ s t i o n In
. ~ ~the tropo-
sphere, the reaction OH + H, is prototypical of an important
class of H-atom abstraction reactions involved in many chain
processes which oxidize H, , CH, and other hydrocarbons to
H 2 0 . The same reaction is also particularly relevant in com-
bustion chemistry, acting as the chain-propagation step in H,
combustion and representing the main source of H,O in
L I
reaction coordinate
Fig. 5 Energy level and correlation diagrams for the reactions
(a) OH + D, + HOD + D and (b) OH + CO + C O , + H, shown
on the same energy scale. The topology along the reaction coordinate
reflects the ab initio results. The arrows mark the energies of experi-
mental investigations.

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
typical hydrocarbon + air flames at atmospheric pressure.
The reaction OH + CO is one of the most important reac-
tions in all tropospheric chemistry, representing the main
removal pathway of OH radicals, and is considered the
second most important reaction in combustion chemistry,
acting as the last step in the oxidation of hydrocarbons.
Because of this practical interest, the kinetics of both reac-
tions have been studied very extensively over the last 20
years. Kinetic bulk experiments carried out in various labor-
atories have measured rate constants and isotope effects over
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an extended temperature range.71,85*86*92 The effect of ini-
tial vibrational excitation of the reactants on the reaction
rate was also explored in state-resolved kinetic
s t ~ d i e s . ~ Reviews
~ ~ ~ ~of- the~ ~ reaction
~ ~ ' ~kinetics
~ ~ are
available." At room temperature the reaction OH + CO is
'
slow (k298 = 1.5 x 10- l 3 cm3 molecule- s- ') and OH + H,
is very slow (k,,, = 6.1 x cm3 molecule-' s-');
however, both reactions exhibit a non-linear Arrhenius
behaviour at high temperat~re.~ 1*85,86*92 The experimental
activation energy is 16.7 kJ mol-' for OH + H, (22.2 kJ
mol-' for OH + D,),86 while only 1-2 kJ mol-' for
OH + C0.71,92The large isotopic effect on the rate constant
points to large tunnelling contributions at low temperatures.
In the case of OH + CO, since the early work which found
the rate constant to be pressure dependent, the reaction
kinetics has been interpreted as proceeding via an energized
HOCO intermediate which may dissociate to products or
redissociate to reagents or be stabilized by collision^.^^^^^
The HOCO species was detected in low-temperature matrices
about 20 years ago,154but only very recently it was observed
in the gas-phase and this has allowed accurate spectroscopic
studies.'55 Lately, the thermochemistry' 5 6 and kinetics' 57 of
HOCO have also been investigated.
The importance and prototypical nature of these two reac-
tions have also encouraged a variety of state-of-the-art
dynamic experiments in recent years.32*34v66-69*7 1-78980-8 by the same a ~ t h o r s at~ a~translational ~ ~ ~ * ~energy~
All of them, however, have focused on the reverse endo-
thermic processes :
H + H,O 4 OH + H,; AH: = 61.9 kJ mol-'
and
H + CO, --t OH + CO; AH: = 102.5 kJ mol-'
(and isotopic variants), By exploiting the hot H-atom tech-
nique, absolute reactive cross-sections and OH internal state
distributions were measured in a wide energy range (ca. 130-
260 kJ mol- ') by many authors in gas-phase,66*72+73*75,76quality, large-scale polarization configuration interaction
and also in van der Waals complexes76 in the case of
+
H CO, , using pump-probe laser techniques. In pioneering
work Zewail and c o - w o r k e r ~and
, ~ ~more recently also Wittig mol- ' (the vibrationally adiabatic threshold is 24.7 kJ
and c o - w ~ r k e r s ,determined
~~ the lifetime of the HOCO
complex using real-time probing, on the pic-femtosecond
time scale, of the OH product from the photoinitiated reac-
tion in a van der Waals complex:
(XH-C0,) OH + CO + X (X = Br, I)
The inelastic scattering of CO, from hot H atoms has also
been investigated.
A series of elegant experiments involving selective initial
excitation of the local OH stretching mode of H,O (HOD)
have explored the effect of vibrational excitation on the reac-
+
tion H H,O. Crim and c o - ~ o r k e r have s ~ ~ studied the reac- clusion from all of these studies was that translation is the
tions of thermal H atoms with H,O and HOD possessing
several quanta of vibrational energy and found a dramatic
mode selectivity. Zare and co-workers68 have studied the
reactions of hot H atoms with HOD and D,O containing
one or two quanta of vibrational energy and found large dif-
ferences in the product branching ratios for the HOD(001)
View Article Online
583
and HOD (100) reactions, depending on whether the OH or
O D local mode was vibrationally excited. These studies
provide the first examples of bond-specific and mode-selective
chemical reactions. The observed effects have been examined
theoretically by Kudla and Schatz, using quasiclassical trajec-
t o r i e ~ , " ~and by C l a r ~ and ' ~ ~by Bowman and Wang,53
using reduced-dimensionality quantum-mechanical treat-
ments. Very recently, the H D product internal state distribu-
tion has also been measured68bfor the H + D,O reaction at
'
an energy of about 260 kJ mol- and examined theoretically
by Kudla and Schatz'58b by QCT calculations. The inelastic
rovibrational excitation of H,O by 213 kJ mol-' H atoms
has also been i n v e ~ t i g a t e dand
~ ~ theoretically examined.' 5 8 b
Elegant as these dynamic experiments on the reverse reac-
tions are, they have not provided detailed information on the
PES along the minimum-energy path.
Experimental information on the dynamics of the direct
processes [reactions (1) and (2)] is much more limited. For
both OH + H, and OH + CO the only information avail-
able came from early flash photolysis s t u d i e ~ ~ ' *coupled ~ ~ ' ' to
time-resolved IR detection, which did not observe any IR
emission from H,O or CO, product and therefore concluded
that H,O and CO, are formed mainly in their ground vibra-
tional state. In a recent flash photolysis study Smith and co-
w o r k e r ~ , ~ using tunable diode laser absorption, found that
a mere fraction of the total energy available to the H + CO,
products is channelled into vibration at room temperature.
Very recently, Wolfrum and co-workers" have measured
absolute reactive cross-sections of 0.08 & 0.03 A' and
0.60 & 0.30 A' for reaction (1) at a collision energy of 16.3
and 21.3 kJ mol-', respectively, and of 0.22 k 0.05 A2 and
+-
0.43 0.09 A' for the isotopic variant OH + D, + HOD
+ D at an energy of 21.3 and 35.6 kJ mol-', respectively.
Partially state-selected integral cross-sections of 1.15 rfr 0.3
and 0.28 rfr 0.08 A' have been also measured for reaction (2)
of 109
and 79 kJ mol-', respectively. In these experiments, where
H(D) atoms are detected, the OH radicals are generated by
UV photolysis of H,O, and are rotationally very hot, while
H,, D, and CO have a thermal rotational distribution.
Inelastic collisions of OH by H, and by CO have been inves-
tigated in crossed beams160.'61 in connection with their
importance in astrophysics.
Much theoretical work has been carried out during the
last few years on both reactions. Walch and Dunning were
the first to examine the OH + H, system by performing high-
~alculations'~ on~ the barrier height and transition-state
geometry for HHOH. The calculated barrier height is 25.9 kJ
mol-') and the saddle point is found to have a coplanar
geometry and to be located in the entrance channel (see Fig.
5). Schatz and E l g e r ~ m a obtained
'~~ an analytic PES, based
on a fit of the ab initio points, and carried out QCT calcu-
lations to determine product vibrational distributions, as well
as rotational, angular and projection distributions of the
H,O product.'62 Schatz and co-workers have also explored
the effects of reagent vibrational excitation on reactivity. 6 3
Slightly improved versions of the Schatz-Elgersma surface
were used in other QCT calculations by Rashed and
and by Harrison and M a ~ n e . ' ~The ' ~ main con-
most efficient form of energy for promoting reactivity, in line
with Polanyi's general vibrational excitation of H,
has a moderate effect, while vibrational excitation of OH and
rotational excitation of either or both reagents has very little
effect on reactivity. Transition-state theory has also been
applied to this reaction by Schatz and W a l ~ h , by ' ~ ~Isaacson

584
and T r ~ h l a r , ’and
~ ~ more recently, by Handy and co-
worker~.~~~
Recently, quantum-mechanical scattering calculations of
rate constants, integral cross-sections, and differential cross-
sections were performed for the first time by Clary41*42and
by Nyman and C l a r ~on~both ~ OH + H, and O H + D,,
using the Schatz-Elgersma surface, while reaction probabil-
ities were reported by Wang and Bowman.53 These theoreti-
cal works do not treat the reaction in its full dimensionality,
but rather use reduced-dimensionality scattering calculations
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or calculations with constrained geometry to reduce the
number of degrees of freedom from six to a maximum of
three. Recently, Echave and C l a r obtained
~ ~ ~ reaction prob-
abilities for the coplanar reaction, i.e. for reaction (1)in which
the system is constrained to be in a plane (four dimensions).
Zhang and ZhangS0*” have taken a step further by reporting
accurate quantum calculations in a five-dimensional space for
total angular momentum J = 0, using time-dependent
methods and the same PES used by Schatz, by Clary and by
Bowman. Baer and co-workersS4 have carried out collinear
and full-dimensional quasi-breathing sphere quantum studies.
Lately, Miller and c o - w ~ r k e r sperformed
~~ exact (six-dimen-
sional, J = 0) quantum thermal rate calculations for reaction
(1). Very recently, Zhang and Zhang,” and NeuhauserSs
simultaneously, reported exact 6D time-dependent initial-
state selected studies on OH + H,, providing reaction prob-
abilities for J = 0, while Balakrishnan and Billing56 have
calculated integral cross-sections and rate constants within a
semiclassical wavepacket approach. Lastly, Bradley and
Schatz” have carried out a detailed quasiclassical trajectory
study of product energy and angular distributions in OH
+ H, and OH + D, and have compared their results with
experiment and quantum reduced dimension results.
Good quality ab initio calculations on the PES of
OH + CO have also been carried o ~ t . ’ ~ ~An * ’ empirical
~’
PES based on a fit to the ab initio points was used to carry
out detailed QCT studies.’ 50b Cross-sections for HOCO
complex formation, product energy partitioning, HOCO life-
time distributions, and thermal rate constants were calcu-
lated. The theoretical surface exhibits no entrance channel
barrier and an exit channel barrier of about 12 kJ mol-’ and
20 30 40
- O , ,,/degrees
Fig. 6 HOD and CO, product laboratory angular distribution from (a) OH + D, -P HOD + D and (b)OH + CO CO, + H reactions at
E, = 26.4 and 59.0 kJ mol-’, respectively. (-) Calculated angular distributionwith the best-fit c.m. translational energy and angular distribu-
tions. The circle in the Newton diagram delimits the maximum HOD and CO, speeds, assuming that all available energy goes into translation.
View Article Online
J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
the saddle point for addition of OH to CO is early and
broad, while the saddle point for elimination of H from
HOCO is very narrow (see Fig. 5). These features suggest the
importance of tunnelling, which should play a significant role
at low collision energies. Quantum scattering calculations
within the rotating-bond approximation, similar to those
carried out for OH + H, and D,, have been very recently
carried out also on the O H + CO reaction by Clary and
S ~ h a t z Within
. ~ ~ a three degrees-of-freedom model, which
accounts for the vibration of OH, the rotation of CO, and the
bend and local stretch vibration of CO,, state-selected inte-
gral and differential cross-sections, rate constants and life-
times of the HOCO complex were computed. Kudla and
Schatzs9 have instead carried out a detailed full dimension
QCT study of reaction (2).
To contribute to the understanding of the dynamics of
reaction (1) and (2), we have quite carried out
reactive differential cross-section measurements in CMB
experiments and determined the spatial distribution and
energy distribution of the products. In the following, the
results of the scattering experiments will be discussed and
compared with the results of quasiclassical and quantum-
mechanical (approximate) dynamical computations on ab
initio surfaces, which have been carried out by Schatz and by
Clary at the experimental energies in what has been, and still
is, a stimulating and fruitful encounter between experiment
and theory.
4.1 Experimental Results
Now let us summarize our experimental results. For obvious
reasons of simpler detection, we have studied the isotopic
variant :
OH + D, + H O D +D
of reaction (1) and used a beam of ‘*OH to improve the
signal to background ratio.
In Fig. 6 we report the lab angular distributions of the
HOD product from reaction (1) at E, = 26.4 kJ mol- and of
the CO, product from reaction (2) at E , = 59.0 kJ mol-’,
together with the corresponding most probable Newton
0 10
I
I
20 1 30 40 ,
;
50
@,,,/degrees

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
diagram. The lab angle 0 is measured from the OH beam. In
the c.m. coordinate system, 8 = 0" is the direction of the OH
beam and represents the forward direction with respect to
OH. The circle in the Newton diagrams represents the
maximum c.m. speed for the heavier reaction product (HOD
and CO,) assuming that all the available energy (collision
energy + reaction exoergicity) goes into product translational
energy. The experimental results for the two reactions are
shown comparatively in the same figure, so that the reader
can immediately appreciate the difference in the dynamics. As
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can be seen the HOD angular distribution peaks sharply to
the right of the c.m. angle, indicating that the product is thor-
oughly back-scattered. Instead, the CO, lab angular distribu-
tion exhibit a quite broad backward-forward structure with a
clear preference for more forward scattering. This suggests
that the reaction is proceeding through the formation of an
intermediate complex and that a large fraction of the avail-
able energy is released into translation. The angular distribu-
tion measurements were accompanied by product velocity
distribution measurements at selected angles and, uia a
forward convolution procedure, the product translational
energy and angular distributions in the c.m. system were
derived, by using a separable form for the c.m. frame product
flux distribution, I&?, E') = T(O)P(E').Although coupling
between the energy and angular distributions is expected to
occur for some reactions, for the systems under study the
uncoupled approximation appears to be satisfactory within
the sensitivity of the present experimental data. The best-fit
c.m. angular, T(8),and translational energy, P(E'), distribu-
tions are shown with continuous lines in Fig. 7 and 8. The lab
angular distribution calculated with the best-fit c.m. functions
are reported as solid lines in Fig. 6.
As can be seen from Fig. 7, the c.m. angular distribution,
T(8), peaks in the backward direction (8 = 180°) for the
HOD product from OH + D,, while shows an asymmetric
1.o
n
s T(8 = 18Oo)/T(8= 00)= exp[ -(zr/2z)]. A reasonable esti-
cz 0.5
o,ol I
L--l,-,J -
.--J--l.--+LJ I Kudla and Schatz" by QCT computations of the opacity
0 90 180
B/deg rees
Fig. 7 Centre-of-mass HOD and CO, product angular dis-
tributions for (a) OH + D , - + H O D+ D and (b) OH
+ CO --* [HOCO] --* CO, + H reactions at E, = 26.4 and 59.0 kJ
mol- ', respectively. (-) Experiment (shaded area delimits the
range of c.m. angular functions which give acceptable fits to the
data), (-. .) quasiclassical trajectory calculations by Bradley and
Schatzs7 for (a) and by Kudla and SchatzS9for (b), (---) quantum
mechanical (approximate) scattering calculations by Nyman and
for (a) and by Clary and S c h a t ~for~ (b).
~ Zewail and c o - ~ o r k e r sand
View Article Online
585
1.o
0.5
0.0
n
0
&/kJ mol- *
Fig. 8 Product translational energy distributions for (a) OH
+ D, +HOD + D and (b)OH + C O + C O , + H at E, = 26.4 and
',
59.0 kJ mol- respectively. (-) Experiment, (---) quasiclassical
trajectory calculations by Kudla and Schatzs9 for (b).AH marks the
reaction exoergicity and E,,, the total available energy.
backward-forward structure, similar to the lab data, for the
+
C 0 2 product from O H CO. This indicates that the reac-
tion OH + D, is a direct chemical reaction dominated by
collinear, or nearly collinear, geometries, while the reaction
OH + CO goes through a complex intermediate, HOCO,
living a time comparable to its rotational period.
Note that the T(8)of the HOD product bears strong simi-
+
larities with that measured for the isoelectronic F D, reac-
+
tion,17 for D + H,,63 and for C1 D,, suggesting that the
PESs of these systems have a similar topology in the critical
region. All the above abstraction reactions appear to proceed
dominantly through collinear, or nearly collinear, geometries,
and the nearly collinear transition state gives rise to pro-
nounced rebound dynamics, at least at low collision energies.
The OH + H, reaction is therefore a simple hydrogen trans-
fer reaction in which formation of the new bond occurs
simultaneously with the breakage of the old bond.
As in other complex forming reactions, which proceed
through the formation of a long-lived complex, the asym-
metry in the T(8)of the CO, product can be attributed to a
lifetime of the HOCO complex comparable to its rotational
period and the 'osculating model' of Herschbach and co-
workers'66 allows us to estimate the complex lifetime.
According to the model, the asymmetry in T(8) is related
to the ratio of the mean complex lifetime, z, to its rotational
period, zr, which is used as a clock, through the relation
mate of the rotational period z, = 2x1/Lm,, was made using
the ah initio geometry'50b to calculate the moment of inertia,
I, of the rotating complex and using the maximum impact
parameter, b,,,, for complex formation (1.6 A, obtained by
function) to calculate the maximum angular momentum, L ,
(L,,, = pub,,,, where p is the reduced mass and u the rela-
tive velocity). From the experimental c.m. angular distribu-
tion backward to forward ratio and the calculated rotational
period, a lower limit of 0.6 ps for the mean complex lifetime
'
at E , = 59.0 kJ mol- was obtained (the lifetime is found to
increase to 1.0 ps at E , = 36.0 kJ mol-I). These estimates
compare well, within the experimental uncertainty of the dif-
ferent experiments, with the lifetime values measured by
~ ~ by Wittig and c o - ~ o r k e r sat~ ~

586
comparable energies from real-time studies of the reverse van
der Waals impacted reaction and with the values calculated
quasiclassically by Kudla and S c h a t ~ ~ *and ~ ~ 'quantum-
mechanically by Clary.43*1 ''
As can be seen from Fig. 8, the product translational
energy distribution for the OH + D, reaction peaks at about
25 kJ mol- ',while the average product translational energy
is 29.7 kJ mol-', that is, about 32% of the total available
energy is found to be disposed as product translational
energy. In the computation of the total available energy the
Published on 01 January 1995. Downloaded by University of Texas Libraries on 30/05/2014 00:36:03.
internal energy of the reactants (estimated ca. 3 kJ mol-') is
also included. This suggests that a large fraction of the avail-
able energy is released into vibrational excitation, since only
moderate rotational excitation is expected for this nearly col-
linear dominated reaction. Similar effects were also observed
+
in the similar F D, r e a ~ t i o n . ' ~
Instead, for OH + CO, the product translational energy
distribution at E , = 59.0 kJ mol-' peaks at about 117 kJ
'
mol- and is very broad. The average fraction of total avail-
able energy released into translation is 0.64 at this high E , (it
increases to 0.70 at the lower E , of 36.0 kJ mol-I). This indi-
cates the existence of strong repulsive forces between H and
CO, after the saddle point is passed. The average product
translational energy (ca. 105 kJ mol-') is similar at both E ,
investigated and closely represents the height of the exit
barrier with respect to the H + CO, product asymptote (see
Fig. 5), i.e. the repulsion in the exit channel disposes essen-
tially all the potential energy associated with the high exit
barrier into translational motion of the products. From
energy conservation one gets that only 36% of the total avail-
able energy is disposed into internal (rovibrational) energy.
Angular momentum partitioning arguments" suggest that
for this mass combination, the initial orbital angular momen-
tum L is essentially converted into final rotational angular
momentum j ' . By assuming L ej' using the maximum
impact parameter for the reaction of 1.6 A (calculated by
Kudla and S ~ h a t z ~one~ ) , derives that the average product
OH L D ,
Fig. 9 Centre-of-mass flux (velocity-angle) contour map of the HOD and CO, products from (a) OH + D, +HOD + D and (b) OH
+ CO CO, + H reactions at E, = 26.4 and 59.0 kJ mol-' respectively
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J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
rotational energy is about 42 kJ mol- ',that is about 25% of
the total available energy (of course, this fraction of energy in
rotation has to be considered as an upper limit). This leaves
only 11% (ca. 17 kJ mol- ') of the total available energy which
can be carried away in vibrational degrees of freedom, with
the conclusion that essentially only the CO, bending (010)
can predominantly be excited, with the symmetric stretch
(100) and two quanta of bending (020) being barely accessible.
This result is corroborated by the flash-photolysis study of
Smith and c o - w o r k e r ~ , ~who
~ * *found
~ very little CO, vibra-
tional excitation ( <6% of the available energy, correspond-
ing to the first bending only). The very weak vibrational
excitation suggested by the CMB and flash-photolysis results
appears to support a transition state HO-C-0 geometry
more collinear than indicated by the ab initio calcu-
l a t i o n ~ . ~ ' ~The
* ' considerably high rotational excitation
determines the mild polarization of the c.m. angular distribu-
tion [see Fig. 7(b)] and is consistent with the bent H-OCO
geometry of the ab initio transition state,lJobin which the H
atom leaves at about 45", with respect to the centre of mass
of the HOCO, thus exerting a strong torque to the CO,
moiety.167
+
The results discussed above for OH D, and OH CO +
are well presented in the product flux (velocity-angle) contour
map representations shown comparatively in Fig. 9. In this
figure one can immediately see how the reaction product
(HOD or CO,) is spatially and energetically distributed in
the c.m, system. This is how an observer sitting on the centre-
of-mass would see the product distributing itself after the
reactive collision between the OH radical and the molecular
reagent. In the case of HOD, it is clearly evident how the
product is strongly backward scattered with respect to the
OH direction, with the peak well within the limit of energy
conservation (the dashed circle) which implies a modest
translational energy, and consequently high internal energy,
of the product. While, in the case of CO, (i) the backward-
forward structure of the angular distribution with a forward
180°
180" A

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
bias, which witnesses the formation of an 'osculating
complex' (ii) the marked confinement of the peaking of the
angular distribution at the limit of energy conservation,
which witnesses a 'high product translational excitation' and
(iii) the near isotropy (i.e. mild polarization) of the angular
distribution, which witnesses a 'high product rotational
excitation', are all clearly observed.
4.2 Comparison between Experiment and Theory
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Let us now compare the results of the scattering experiments
with those of dynamical calculations on the ab initio PESs.
4.2.1 OH + D, + H O D + D
To date, among the various theoretical approaches so far
devised for the four-atom reactive scattering problem, only
the reduced dimensionality treatment of has pro-
vided differential cross-sections for four-atom reactions.
Nyman and C l a r ~ have
~ ~carried out calculations for the
OH + D, reaction at several energies, including the energy of
our experiment, using the ab initio (Schatz-Elgersma) surface,
and have found a completely backward-scattered HOD
product at E , = 26.4 kJ mol-'; the calculated angular dis-
tribution is in very good agreement with the experimental
determination (see Fig. 7). Instead, the calculated fraction of
energy released in translation is 0.71, which disagrees strong-
ly with respect to the experimental value of 0.32. The dis-
agreement suggests that the PES has some shortcomings and
may need improvement, or that some of the approximations
in Clary's quantum method are not warranted, or both. Note
that very recent 6D quantum rate constant cal-
c u l a t i o n ~ ~ ~ *on~ 'the
- ~ same
~ PES are in considerable dis-
agreement with the approximate quantum results of
and also with experimentE6 (by a factor of 3 at
room temperature). This casts some doubt both on the
approximations of Clary's method and on the adequacy of
the Schatz-Elgersma PES for OH + H, .
The very recent quasiclassical trajectory calculations by
Bradley and S ~ h a t of z ~the
~ angular distribution and energy
partitioning for the O H + D, reaction at an energy of 28.8 kJ
mol-', which is close to the experimental energy of 26.4 kJ
mol-', are essentially in line with the approximate quantum
results of Nyman and C l a r ~ the : ~ ~angular distribution is
found to be slightly narrower than the quantum results, but
still in good agreement with experiment (see Fig. 7), and the
fraction of energy in product translation somewhat smaller
(0.47) than the quantum result (0.71), but still in considerable
disagreement with respect to the experimental value of 0.32.
This again suggests that some inadequacies are present in the
PES, which gives too little product internal excitation. The
present shortcomings of the Schatz-Elgersma PES'48*14'
have been discussed in ref. 158b and 57. Clearly, the part of
the PES that controls the energy release needs a detailed
scrutiny by sophisticated ab initio means. That something is
not quite correct is also suggested by the fact that QCT rate
calculations' 589168 for vibrationally excited H,O reacting
with H atoms give smaller rate enhancements than those
found experiment ally.
There is clearly a need for a more accurate PES and for
exact quantum scattering calculations. A new potential
surface for modelling the dynamics of the OH + H, reactions
has been recently proposed by I s a a c s ~ n . 'This~ ~ new poten-
tial form not only reproduces the ab initio results of Walch
and Dunning,148 but also the new barrier shape computed by
Dunning et ~1.''' It differs somewhat from the earlier form
devised by Shatz and Elger~ma,'~'which has been used until
now in QCT and quantum dynamical calculations. Since
both barrier shape and the degree of reaction path curvature
View Article Online
587
strongly influence the rate constant^,'^' it would be inter-
esting to examine the effects on the dynamics as well. Very
large scale, high quality, ab initio calculations of a new PES,
on the line of those recently reported for the isoelectronic
+
reactive system F H,, have been very recently completed
+
for OH H, by Werner,17' and will soon be tested in
'
dynamical calculations. 72 Exact quantum dynamical calcu-
lations of the double differential cross-sections for OH + H,
(and isotopic variants) may be, in a few years, within reach of
the ever faster-growing computer capabilities. The exact cal-
culations are, of course, required for testing the various
dynamical approximations and for an unambiguous test of
the ab initio PES.
+
4.2.2 OH CO +CO, +H
The comparison between theory and experiment for the
energy partitioning and angular distributions of the
OH + C O reaction reads as follows. In Fig. 7 the experimen-
tal c.m. angular distribution at E, = 59.0 kJ mol-' is com-
pared with the results of QCT calculations by Kudla and
S ~ h a t z ~5~0 pand
' of approximate quantum calculations by
, ~ ~ the same ab initio surface. As can
Clary and S ~ h a t z using
be seen, the quantum treatment gives an angular distribution
with strong backward and forward peaking, with a slight
preference for forward scattering. This sharp polarization of
the quantum differential cross-section, with nearly no inten-
sity outside a small angular region close to 0 = 0" and 180",
is attributed to the pronounced resonance-like structure of
the quantum reaction probability function which translates in
a few partial waves for large total angular momenta contribu-
tion to the scattering. It appears that a model comprising
three degrees of freedom is inadequate to describe the
OH + CO reactive scattering. The comparison in Fig. 7
shows that the angular distribution calculated by Kudla and
Schatz by the full-dimensional QCT method is in close,
although not quantitative, agreement with experiment. The
still noticeable discrepancy between QCT results and experi-
ment has to be traced back to some inadequacies of the
+
potential surface for the O H C O reaction.
The rotating-bond-approximation quantum calculations of
Clary and S ~ h a t zgive ~ ~65% of the total available energy
into product translation at E , = 59.0 kJ mol-', in good
agreement with experiment and the QCT results of Kudla
and S ~ h a t zgive ~ ~about 60% at this same E,, also in fair
agreement with experiment. The good agreement between
experiment and QCT results extends to the full shape of the
translational energy distribution function, as can be noticed
in Fig. 8. However, both quantum43 and QCT calcu-
lations'50~'56predict more energy in vibration than in rota-
tion, which is at variance with the results of both the CMB
study (see above) and the flash-photolysis e ~ p e r i m e n t . ~ ' ~ * ~
In conclusion, there appears to be some disagreement
between experiment and theory, which points to some
inadequacies both in the PES and in the dynamical approx-
imations of the quantum treatment. The existence of short-
comings in the PES are also suggested by the poor
comparison between experiment and calculated rate con-
stants as a function of t e m p e r a t ~ r e .Clearly,
~~ an improved
PES is needed, especially in the region of the tight transition
state in the exit channel. On the dynamical side, full-
dimensional quantum reactive scattering calculations are of
course desirable. This would require the treatment of all the
rovibrational modes of the reactants and products, including
the O H and CO, rotations, and would permit a clear test of
the ab initio PES. Although, at present, exact scattering cal-
culations for O H + CO appear to be out of reach of even the
most advanced computer capabilities, they may become feas-
ible in the not too distant future.
 View Article Online

588 J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91

5. Effect of Electronic Excitation on Reaction
Dynamics
Electronic energy, in contrast with rotational and vibrational
energy, is a peculiar form of internal energy which promotes
a reaction on a potential surface which is different from that
of the ground electronic state. In general, the different energy
and topology of the excited PES determine a completely dif-
ferent reactivity and dynamics of the system. We examine
here the effect of electronic excitation on the reaction
dynamics of atomic oxygen.
Published on 01 January 1995. Downloaded by University of Texas Libraries on 30/05/2014 00:36:03.
reported until recently, when we undertook in our laboratory
a systematic investigation of O('D) reaction dynamics.
We have investigated the reaction dynamics of O('D) with
the series of hydrogen halides (HCl, HBr and HI)'2'*'269'79
using supersonic beams containing both O(3P) and O(lD).
Reactive differential cross-sections have been measured for
the reaction channel leading to H displacement, exploiting
the fact that this channel is strongly endoergic for q 3 P ) . For
+
O('D) HBr, a detailed study of both possible reaction
channels, leading to BrO + H and OH + Br, was carried out

in collaboration with Sloan's laboratory in Waterloo'26

The kinetics of atomic oxygen reactions, because of the
great relevance in areas of practical interest such as atmo-
spheric and combustion chemistry, has been widely investi-
gated. Less information is instead available at the
microscopic dynamical level, especially for the reactions of
oxygen atoms in their first electronically excited state 'D,
located 190 kJ mol-' above the ground state 3P. It is worth
recalling that O('D) is the main photolysis product of ozone
in the stratosphere and upper troposphere at wavelengths
<310 nm and is a metastable species with a lifetime of about
150 s . ' ~ * ' ~ * ' Although
'~ its main fate in this environment is
physical quenching to O(3P) by 0, and N,, a small but sig-
nificant fraction of it reacts at nearly gas collision rate with
trace level species such as H20, H,, CH4, N,O, hydrogen
halides and pollutants such as chloro-, bromo- and fluoro-
carbons, creating highly reactive radical products which are
responsible for significant reduction of the Earth's ozone
layer. It is known that O(3P) and O('D) react differently in
the gas phase with the rate constants of O('D) reactions
being typically many orders of magnitude larger than for
ground-state O(3P),'08b*'13 thus making the role of O('D) in
many processes much more important than its little abun-
dance would suggest.
A survey of the pertinent literature shows that O('D)
atoms are usually generated photolytically, either in cell or in
beam, by using high-power pulsed UV lasers and the reaction
products are probed spectroscopically,either by IR chemilu-
minescence, LIF or REMPI. This has often confined the
studies to the determination of internal energy distributions
of OH and NO product forming c h a n n e l ~ . ~ ~ Re - ' 'cently,
~
the O('D) reactions with N,O, CH, and HCl have been
studied by Simons and c o - ~ o r k e r sin~ bulb,
~ relative to NO
and OH formation, uia the production of velocity-aligned
O('D) atoms using sub-Doppler polarized LIF to probe the
products and determine their scalar quantum state distribu-
tions and vector correlations, The dynamics of the reaction
O('D) + N,O and, more recently, also those with HC1 and
C1, have been studied in laser-initiated half reactions within a
pulsed beam by LIF of the molecular product and also by
REMPI of the atomic p r o d ~ c t . " ~The ~ ' ~reactions
with methane and propane monomers and clusters have
~
using the complementary techniques of CMB and fast-time-
resolved Fourier-transform spectroscopy.
In cases in which the various reaction channels are exo-
ergic for both O(3P) and O('D), as in O(3P,'D) H,S, con- +
tribution from both electronic states of oxygen to the reactive
scattering signal can be expected under our experimental con-
ditions,"' at least at energies above the barrier for O(3P)
(usually always present). By exploiting the availability of cw
supersonic beams containing both O(3P)and O('D), we have
performed a detailed study of the effect of electronic excita-
tion on the reaction dynamics of atomic oxygen under the
same experimental conditions by performing experiments at
different collision energies: the H-displacement channel
leading to the formation of HSO (see below) was examined.
5.1 o ( ~ P , ~ D ) H,S +
In the reaction of O(3P,'D) with hydrogen sulfide three differ-
ent channels are energetically open :
O(3P)+ H,S + H; AH; = -16.7 kJ mol-'
-+ HSO (34
O(lD) + H,S -+ HSO + H; AH: = -206.7 kJ mol-' (3b)
O(3P)+ H,S + OH + SH; AH; = -49.3 kJ mol-' (44
O('D) + H,S + OH + SH; AH: = -239.3 kJ mol-' (4b)
O(3P)+ H,S + SO + H,; AH; = -53.4 kJ mol- ' (54
O('D) + H,S SO + H,; AH; = - 98.8 kJ mol-'
--+ (5b)
Fig. 10 portrays the reaction coordinate diagram with the
energetics also-outlined.These reactions are prototypical for
the oxidation processes of sulfur compounds and therefore,
besides their interest for basic chemical kinetics and
300
k
m a
x

recently been investigated in pulsed crossed beam experi-

ments using LIF detection of the OH product at the collision
of O('D)

7
2ooF
-7
100
I
Emn o ( ~ D+)H ~ S

tEm~
centre.'75 Very recently, with O('D) generated by photolysis €
of an ozone beam seeded in a rare g a and using
~ sub-~ ~ ~ ~ ~ ~ ~
Doppler REMPI detection of the H atom, the dynamics of
the reactions O('D) + D, and HD has been studied in pulsed
-100o~
crossed beams. The dynamics of O('D) + H2, D2 and HD
c
0)

t
has also been investigated by both REMPI and LIF tech-
niques in a pulsed beam,' " while integral reactive cross-
sections have recently been measured by Wolfrum and
co-~orkers.''~Reactive DCS by the CMB method with -200
-300
mass-spectrometric detection were first measured by Lee and
co-workers"' in pioneering work on O('D) + H, and O('D) reaction coordinate
+ CH, in 1980, following the developing of continuous Fig. 10 Energy level and correlation diagram for the O('P,'D)
supersonic beams of O('D) by the RF discharge method. No
other reactive DCS measurements by this technique were + H,S system. Eminand E,, delimit the range of experimental colli-
sion energies.
 View Article Online

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91 589

dynamics, are also of relevance in atmospheric and com-
bustion chemistry.
The SO + H, channel has not been observed with O(,P) in
kinetic studies, presumably because of the high potential
barrier which characterizes three-four centre molecular
hydrogen elimination processes (this is shown schematically
in Fig. 10). Recently, our results' 18,180*181 have confirmed
this and have established that SO + H, formation does not
even occur upon electronic excitation of the oxygen atom to
the 'D state for collision energies up to 49.4 kJ mol.-'
The OH + SH channel from the O(3P) reaction has been
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of the product under high-resolution conditions. 8*179-181 ''
Fig. 11 shows the HSO product angular distributions at four
different collision energies, and Fig. 12 shows TOF spectra
'.
for the highest collision energy of 49.4 kJ mol- An ample
publication on this study, which includes all the data sets at
the six energies investigated is currently under prep-
aration.18' An overview of the main results is presented here.
As can be seen from Fig. 11, the lab angular distribution at
E , = 14.2 kJ mol-' shows a symmetric backward-forward
structure around the c.m. angle. At this energy, only O('D) is

studied extensively from a kinetic point of vie^"^*'^^ and is
thought to account for about 50% of the overall reaction [the
room-temperature rate constant for reaction (4a) is
1.8 x cm-, molecule-' s-' and the activation energy
18.0 & 1.7 kJ mo1-'].'84,'85 Therefore, the HSO + H reac-
tion, channel ( 3 4 , accounts for the remaining 50% of the
overall O(,P) reaction. The rate constant at room tem-
perature for the O('D) reaction has been rneasuredlE6 and
found to be nearly gas kinetic ( k = 2.2 x lo-'' cm-,
molecule-' s-'); the OH + SH channel is found to account
for about 26% of the overall reaction, which suggests that the
HSO pathway is the most important reaction channel in the
reaction of H,S with O('D).
From a microscopic point of view, no dynamical informa-
tion was available on the HSO channel from the O('D) reac-
tion prior to the study from this laboratory, while
information on the HSO channel from O(3P)existed from a
low-resolution CMB study at one collision energy by Grice
and co-workers.'87 Instead the dynamics of the OH channel
from the O('D) reaction has been examined by LIF'02 and
FTR-FTS-IC'" techniques and a combined analysis of these
studies led to a strongly bimodal vibrational distribution,
suggesting that two different microscopic channels are
occurring. However, a more recent work'86 using LIF detec-
tion did not confirm this bimodal OH vibrational distribu-
tion, but rather determined an OH vibrational distribution
similar to that observed in the analogous O('D) + H,, CH,
and NH, reactions. The OH vibrational distribution from
the O(3P) reaction [channel ( 4 4 has been measured by
expected to react with H,S and already the lab data imme-
diately suggest that the O('D) reaction is proceeding through
the formation of a long-lived complex. The same shape of the
angular distribution is maintained at E , = 19.9 kJ mol-',
which is only slightly above the O(3P) threshold, indicating
that negligible O(3P)contribution occurs. Convolution of the
lab data (product angular distribution and TOF distributions
at selected angles) at the two low E , in the c.m. frame leads to
the following conclusion: the HSO product c.m angular dis-
tribution shows a symmetric backward-forward structure
which is attributed to the O('D) reaction proceeding through
the formation of a long-lived complex, presumably a thlo-
peroxide (HOSH) intermediate, following O('D) insertion. A
1 .o
0.5
0.0
1 .o
A

.-E? 0.5
Agrawalla and Setser in a flowing afterglow by IC and LIF C c.m.
techniques.' 8 8 4 0.0
The overall rate of reaction of O('D) is about four orders m
W
1
of magnitude faster than that of O('P). This can be rational- h

ized by considering that the triplet reaction proceeds on the 2

lowest triplet surface with considerable activation energy,
z
1.o
while the singlet reaction takes place on the lowest singlet
surface with virtually zero activation energy. This is in accord
with the accepted behaviour of the two different electronic 0.5
states of oxygen: O(,P) preferentially adding to molecular
bonds giving rise to a triplet intermediate, and O('D) prefer- 0.0
entially inserting into molecular bonds giving rise to a
strongly bound singlet intermediate (see Fig. 10). Dynamic
studies of the OH-forming channel show similarities between
the OH vibrational distribution from the O(,P) and the 1 .o
O(' D) reactions, suggesting that the abstraction-like
dynamics of O('D) may be originating from a singlet-triplet 0.5
surface crossing following the initial insertion of O(' D).'8 8
In our CMB studies of the H-displacement channel, 0.C
angular and velocity distribution measurements of the HSO 0 30 60 90
product were carried out at six different collision energies, @/degrees
starting from energies below the threshold for the ground- Fig. 11 Laboratory angular distribution of the m/z = 49 product
state reaction up to about 50 kJ mol-'. At energies below, or + +
(HSO) from; O('D) H2S HSO H at (a) E , = 14.2 kJ mol-',
--.)

comparable to, the threshold of O(3P), only a contribution
from the O('D) reaction can occur, while, by increasing the
collision energy, a contribution from the O(,P) reaction is
also expected. The two contributions were disentangled by
performing angular and velocity distribution measurements
a = 0 and (b) E , = 19.9 kJ mol-', a = 0; and from O(3P,'D)
+
+ H2S --* HSO H at (c) E , = 34.1 kJ mol-', a = 0.30 and (d)E , =
49.4 kJ mol-', a = 0.70. (-) calculated best-fit c.m. translational
energy and angular distributions from eqn (I) at the indicated value
of a, with contributions from O('D) and O(3P), (---) and (-----),
respectively. ( 0 )m/z = 49.
 View Article Online

590 J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91

able rotational excitation of the product, i.e. a significant (L,

j') correlation. This is not surprising considering the specific
1.o mass combination. A fairly large percentage (about 40%) of
the total available energy is disposed as product translation
at these low collision energies and indicates the presence of a
potential barrier in the exit channel.
As the relative collision energy is raised above 25 kJ
0.0
mol-', the lab angular and velocity distribution data start to
show some structure which is unambiguously related to the
features of the velocity and angular distributions in the c.m.
Published on 01 January 1995. Downloaded by University of Texas Libraries on 30/05/2014 00:36:03.

h
*r
1.0 system of the HSO products from both O('D) and O(3P)
0' reactions."' This is shown in Fig. 11 and 12. A weighted c.m.
s differential cross-section, E') :

0.0
was used in the data analysis, in which the parameter a rep-
resents the 3P contribution. a increases from 0.23 at E , =
28.0 kJ mol-' to 0.70 & 0.05 at E , = 49.4 kJ mol-'. While at
1.o E , = 14.2 and 19.9 kJ mol-' the T(0)of the O('D) reaction is
backward-forward symmetric, at higher collision energies the
distribution becomes more forward symmetric, reaching a
ratio T(6 = 180O) : T(O = Oo) of 0.60 at E, = 49.4 kJ mol-'.
0.0 This finding is interpreted in terms of formation of an oscu-
i ' L $ 1
I lating complex at higher E , The estimated mean lifetime
100 200 300 100 200 300 of the complex decreases from 4.7 rotational periods at E, =
flight time/ps 28.0 kJ mol-' to slightly less than one rotational period at
Fig. 12 TOF distributions of the m/z = 49 product (HSO) produced E , = 49.4 kJ mol-'.'" The strongly forward-biased product-
at lab angles, (a)--Cf), 16,24, 32,42, 48 and 52", respectively, for E, = flux contour map at E , = 49.4 kJ mol-' can be appreciated
49.4 kJ mol-'. (-), (---) and (-----), see Fig. 11. in Fig. 13(a). Here, the mild polarization along the relative
velocity vector, which witnesses a high degree of product
rotational excitation, is also evident.
The O(3P) reaction is found to proceed through a direct
possible sulfoxide (OSH,) intermediate is calculated to be mechanism with pronounced rebound dynamics at all ener-
theoretically less stable by ca. 84 kJ mold' (see Fig. gies investigated. At E , = 49.4 kJ mol-' the c.m. angular dis-
The c.m. angular distribution also shows a mild peaking tribution is completely confined to the backward hemisphere
along the relative velocity vector, which indicates a consider- and the P(E') indicates that a very large fraction (ca. 60%) of

180" O0

i-----i

I 500 m.s-' 500 m s-'

180" A

Fig. 13 Comparison between the c.m. flux (velocity-angle) contour maps of the HSQ product from (a) O('D) + H2S --+ HSO + H and (b)
O(3P)+ H2S + HSO + H, at E, = 49.4 kJ mol-'

J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
the total available energy is released in translation. This sug-
gests that the barrier to reaction is located in the exit
channel. The results obtained for the O(,P) reaction are in
qualitative good agreement with those of an earlier'87 low-
resolution CMB study. The smaller uncertainties in our
work, which are the consequence of a higher resolution, have
permitted us to determine the heat of formation of the HSO
radical with an accuracy of better than 3 kJ mol-'
[AfHo(HSO) = -3.7 & 2.9 kJ m ~ l - ' ] ' ~and ~ to have a
direct insight into the geometric orientations between the
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interacting particles during the reactive encounter, i.e. on the
geometry of the transition state. Specially, a nice example was
provided of how the product c.m. angular distribution of a
direct H-atom displacement reaction can mirror the geometry
of the transition state.'79b A simple model for the direct
rebound dynamics of O(,P) with H,S, as observed in our
experiment at E , = 49.4 kJ mol-', has been recently pro-
posed by Grice and c o - w o r k e r ~ . ' ~ ~
The dramatic difference in the dynamics between the O(,P)
and O('D) reactions can be appreciated in Fig. 13 where the
contour maps of the HSO product from the reaction of
atomic oxygen in the two different electronic states are com-
pared at E , = 49.4 kJ mol- '.
The results obtained from this study on O(,P,'D)
+ H,S --+ HSO + H demonstrate that the triplet reaction
proceeds with a substantial energy barrier via a very short-
lived, weakly bound, triplet intermediate and is characterized
by a direct (rebound) mechanism, whereas the singlet reaction
proceeds with virtually no barrier uia a singlet surface that
correlates with a strongly bound intermediate (presumably
the stable HOSH molecule) and therefore is characterized by
a mechanism forming a long-lived complex. This is a conse-
quence of the different features on the ground and excited
PESs (see the energy-level and correlation diagram of Fig.
10). O(,P) is electrophilic in nature and attacks the out-of-
plane lone-pair orbital of the sulfur atom to form an initial
pyramidal configuration of the transition state, which on dis-
sociation passes through an intermediate planar configu-
ration to minimize exchange repulsion, as suggested by ab
initio calculations'g0~191on the O(,P) + H,S triplet PES.
Atomic oxygen in the ID, state has a diradical character,
which favours the formation of two bonds in H-0-S-H
following an insertion. The rapid escape of one H atom from
both the triplet and singlet intermediates precludes three-
centre H, elimination; this is why the SO + H, channel is
neither observed with O(,P) nor with O('D).
From a general point of view on the mechanism of O('D)
reactions, although they are thought to occur predominantly
via insertion and to proceed via a deep singlet surface, forma-
tion of a long-lived complex has never been observed in
dynamical studies of OH-forming channels, In contrast to the
+
O('D) HX (X = C1, Br, I) systems, where the difference in
exoergicity between the H-displacement and the H-
abstraction channels is always very large (170-210 kJ mol-I),
in the O('D) + H,S system, the formation of OH is only 33
kJ mol-' more exoergic than that of HSO (see Fig. 10). If
O('D) inserts into the H-S bond to give a stable, long-lived
HOSH intermediate, which dissociates via the 'A' ground-
state surface and leads to HSO formation (see Fig. lo), one
could also reasonably expect OH formation from the decom-
position of the HOSH complex. However, recent dynamical
studies using LIF techniques of OH energy partitioning from
the reaction O('D) + H,S, found a hot vibrational distribu-
tion, similar to that observed also in other O(lD) reactions
(with H,, CH, and NH,) and interpreted it as arising from a
direct H-atom abstraction process.'86 Clearly, dynamic cal-
culations on realistic PESs are desirable and would help to
clarify the overall picture by elucidating the role played by
View Article Online
59 1
the different triplet and singlet potential surfaces and by non-
adiabatic coupling.
6. Future Prospects
In this Faraday Research Article we have discussed some of
our recent applications of the crossed molecular beams scat-
tering method with mass-spectrometric detection, to the
study of the dynamics of elementary chemical reactions of
atoms and radicals with simple molecules.
The preliminary results on C1 + D, presented here show
that even the important C1 + H, (and isotopic variants) reac-
tion, for which exact quantum dynamical calculations of
state-to-state differential cross-sections are feasible, can be
tackled with experiments at the microscopic level. We think
that it will be useful to perform a systematic detailed CMB
study of these reactions at different collision energies and to
explore directly isotopic effects. The energy dependence of the
integral reactive cross-section (excitation function) can be
determined and the variation of the dynamics with relative
collision energy examined. The results can then be compared
with those of exact 3D quantum-mechanical computations
and so provide a very sensitive test of ab initio and semi-
empirical PESs. Of course, useful complementary information
on the C1+ H, reaction dynamics can be expected from
+
other techniques. The Cl(2P3/2:1/2) H,(D,) system is also a
suitable candidate for exploring, both experimentally and
theoretically, the role of spin-orbit effects on reaction
dynamics, because the spin-orbit splitting of C1 is sizeable
(10.5 kJ mol-') and comparable to the reaction barrier
height (ca. 25 kJ mol- ') and to the HCl(DC1) product vibra-
tional spacing [ca. 33 (25) kJ mol-'I. Preliminary CMB
experiments carried out with C1 beams containing different
ratios of the excited to ground spin-orbit state indicate a pro-
nounced reactivity of C1(2P,I,). By adjusting the relative colli-
sion energy with respect to the threshold, it has been possible,
for instance, to observe the formation of DCl(u = 1) from
only C1(2Pl,,). By measuring the C1 spin-orbit ratio in the
beam by Stern-Gerlach magnetic analysis,'92 it will be pos-
sible to carry out experiments with known concentrations of
C1(2P,12) and Cl(zP,,2) and extract detailed information
about the reactivity and dynamics of the two different elec-
tronic states. The role of spin-orbit states in the F + H, reac-
tion has a long-standing theoretical interest, but so far only
approximate treatments have been proposed. l g 3 Non-
adiabatic effects may need to be accurately included in
detailed comparisons between theory and experiment for the
+
X('P3/2,1/2) H, reactions (X = F, C1, Br, I). Hopefully, a
better understanding of the halogen-hydrogen family of reac-
tions at the microscopic dynamic level will be achieved in the
near future.
Obviously, the work carried out so far on O('D) and Cl
reactions can also be extended to other systems. For instance,
it would be interesting to measure reactive DCS for the reac-
tions of O('D) with simple molecules such as H, and CH4, as
well as with more complex reagents, such as chloro-, fluoro-,
and bromocarbons, relative to the CIO and BrO forming
channels. In the case of the reaction O('D) + H,, which is
amenable to detailed theoretical investigation, improvement
in apparatus resolution may make it possible to attain some
product vibrational state resolution.' 94 The O('D) + H,
reaction dynamics is still not well understood and, in particu-
lar, it is not clear what the relative role of insertion and
abstraction mechanisms are. Additionally, the product vibra-
tion distribution is still somewhat uncertain. BrO formation
has recently been observed in a preliminary study of the
O('D) + CF,Br reaction."' Investigation of the effect of

592
electronic excitation on the dynamics of atomic oxygen reac-
tions, as shown here with H2S, can presumably be extended
to other systems, including other C1 atom reactions, such as
+
Cl CH, (a very important reaction in atmospheric
chemistry).
Undoubtedly, the CMB scattering method will continue to
play a very important role in future reaction dynamics
studies. Particularly exciting is the prospect of using synchro-
tron radiation, as planned in Berkeley,Ig6 to ionize the reac-
tion products in place of the usual electron bombardment.
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The alternative approaches for obtaining reactive DCS are all
based on pulsed photolytic generation of the radical reagent
and different laser spectroscopic detection schemes. Special
mention goes to the new strategy in which state-to-state DCS
can be derived, in favourable cases, from photoinitiated reac-
tions in a pulsed beam or even in a bulb, using velocity-
aligned atomic reagents produced by photolysis and
sub-Doppler product detection, as recently shown by Simons
+
and co-workers3’ for O(’D) N 2 0 , CH, and HCl, and by
Zare and co-workers7 for Cl(2P312)+ CH4(v3= 1, j = 1)30
and Cl(2P3/2)+ CD, . I g 7 Time-resolved measurements of
intramolecular dynamics offer an opportunity to observe a
reaction molecular system during its evolution from reactants
to products and explore in detail the dynamics of transition
states in real-time by using the novel femtosecond spectros-
copy method pioneered by Zewail and c o - w o r k e r ~ All . ~ ~ ~ ~It~is a pleasure to thank past and present co-workers (L.
these techniques, together with the more traditional photoly-
sis pumpLIF/REMPI-probe measurements in a low-
pressure cell (or beam) and from IR chemiluminescence
experiments, will contribute enormously to the advancement
of chemical reaction dynamics.
The results reported here for the diatom-diatom reactions
OH + D2 and OH + CO show the new possibilities of reac-
tion dynamics beyond the atom-molecule systems. However,
a detailed comparison between experiment and theory calls
for further work on these systems. Theory is asked to provide
more accurate ab initio PES via larger scale electronic struc-
ture calculations on one side, and improved algorithms for
more reliable, and hopefully exact, quantum mechanical scat-
tering calculations on the other. Several groups are under-
taking this endeavour, with Werner having just completed
+
the calculation of an improved PES for OH H, and Clary,
Baer, Schatz, Bowman, Billing, Miller, Zhang, Neuhauser,
and others making significant progress on an exact (full six
dimensions) treatment of the four-atom reactive scattering
problem. On the experimental side, reactive DCS measure-
ments should be carried out (and actually are carried out in
our laboratory) at more collision energies and on the isotopic
variants. Information on the internal (rovibrational) energy
distribution of the nascent H,O and C 0 2 products can be
expected in the future as suitable spectroscopic detection
schemes for these molecular products will become available.
The next step will be a move towards even more complex
(polyatomic) reactions. In this regard, experiments with CMB
(and with other techniques) can be extended to the investiga-
tion of the dynamics of other important reactions of the O H
radical, such us those with simple hydrocarbons (CH,, C2H,)
and with halogen-containing molecules. The feasibility of
quantum scattering calculations on polyatomic reactions as
O H + CH4, OH + HCl and OH + HBr has been very
recently demonstrated by Clary and co-workers using the
rotating bond approximation and semiempirical PESS.,~.,~
Obviously, it is important to extend dynamic investigations
to the reaction of other radicals. Great promise for radical
beam generation is offered by pyrolysis or UV laser photoly-
sis of a suitable precursor in a pulsed nozzle expansion, which
has been shown to be able to lead to a selective formation of
many radical^.^^.'^^ Such pulsed radical beams can most
View Article Online
J. CHEM. SOC. FARADAY TRANS., 1995, VOL. 91
conveniently be used in pulsed CMB experiments. An alter-
native hope is to be able to generate continuous supersonic
beams of other radical species, besides OH, by using the same
RF discharge technique and then study their reaction
dynamics via differential cross-section measurements in CMB
experiments with mass-spectrometric detection. Of course,
this method always has the complication of the presence of
other species in the beam and care must be exercised so that
they do not represent interference in the reaction under
study.
We conclude by stressing that an exciting feedback
between theory and experiment has played a crucial role in
the enormous deepening of our understanding of atom and
small radical reaction dynamics which has occurred during
this last decade. The theoretical formalism for handling the
dynamics of atoms and small radical reactions is sufficiently
developed and is ready to be implemented on increasingly
larger systems. Although the calculation of reliable PESs by
ab initio techniques remains the bottleneck in reaction
dynamics, continuous progress is observed and can be
expected. The great amount of experimental and theoretical
work which has been, and continues to be, devoted to simple
reactions, is paving the way to understanding more complex
chemical systems.
Beneventi, L. Dionigi, and E. H. van Kleef) for their valuable
contribution to some of the work discussed here. We also
wish to thank all our colleagues of the Molecular Beam
Group of Perugia for the useful discussions, collaborative
atmosphere and continuous encouragement. We thank G. C.
Schatz, D. C. Clary and A. Lagana for interesting and useful
discussions. Preprints and reprints from G. C. Schatz, D. C.
Clary, J. M. Bowman, W. H. Miller, J. Zhang, M. Baer, C.
Wittig and J. Wolfrum are gratefully acknowledged. Many
thanks go also to A. H. Zewail and C. Wittig for enlightening
discussions on the HOCO lifetime. Financial support from
the Italian ‘Consiglio Nazionale delle Ricerche, Progetto
Finalizzato Chimica Fine’ and ‘Minister0 Universita e
Ricerca Scientifica’, is also gratefully acknowledged. Grants
from EEC, ENEA and NATO (CRG. 920549) made possible
several aspects of the research reported here.
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Paper 4/05539J; Received 12th September, 1994