Volume 34, number 1 CHEMICAL PHYSICS LEl-fERS 1 July 1975

INFORMATION-THEORETIC ANALYSIS OF
QUANTUM MECHANICAL REACTION CROSS SEtXIONS*

Robert E. WYATT*”
DEpartmetIr of Chemistry. University of Texas, Austin, Texas 78712, USA

Received 31 March 1975

Information theory Is used to nnslyze quantum mechanic4 rotation excitation probabililies for the hydrogen exchange
reaction. A linear rotational surprisal is found, and the entropy deficiency of the product rotational distribution is com-
puted.

The information theoretic approach [l-5] to the Lester-Liu [9] H3 potential surface?. The product
role of energy in chemical dynamics has had extensive rotational energy distribution obtained from reactant
recent application to such diverse problems as the molecules in the u = J = 0 state?? will be analyzed at
analysis of branching ratios between alternate prod- E = 0.80eV total energy. Since the product Hz vi-
uct channels [2-41, the selectivity of energy consump- brational ground state energy is 0.273 eV, the energy
tion in reactions [S] , znd the study of specificity in available for product rotation is no larger than E-Eye
product energy distributions [5]. A key feature of = 0.527 eV. The natural variable [I] in terms of
the approach is a comparison between the actual (es- which to analyze the rotational distribution is the
perimental or computed) distribution and a prior sta- frsctiongR. = E;z,/(E-Ev,), where ERp is the product
tistical distribution formulated without detailed dy- rotational energy.
namical information. Anaiysis of specificity in prod- In the absence of any dynamical information on
uct state rotational populations from computalioml the distribution of product rotational levels, what is
studies has so far been based upon results provided the prior expectation of finding molecules in level J’
by classical trajectory calculations [6,7] _The possible when the vibrational and total energies are constrained
role of quantum effects in the analysis has not been to E, and E respectively? It has been suggested that
clear. Experimental rotational distributions have also the microcanonical ensemble [IO] provides a useful
been examined [6,7] , and except for F f HD the re- prior distribution [I] . In such a situation of stntis-
sults were found to be “not very surprising” [7] (in tical democracy, all states in the avaiiable phase space
an information-theoretic sense). are equiprobable, so the expectation of finding both
We wish to present the fist information theoretic the molecule in level J’ (with energy ERo)and the
analysis of quantum mechanical ca.Iculations for a atom-molecule translational energy to be ET, =
chemical reaction. Reaction cross sections for the E-E,. - ER. is proportional to the rotational degener-
threedimensional hydrogen exchange reaction have acy (U’t 1) and to the density of translational states,
been obtained [8] over the post-threshold energy
region (0.60 to 0.85 eV) by integration of large sets 7 Our bending potential is a local two-term Legendre expan-
of closecoupled scattering equations for the Yates- sion of the potential in ref. [9] _The sensrtivity of the re-
sults to the bending potential fit is being investigated.
?i The total energy is measured from the bottom of the en-
tcaaca (or exit) valley. and thus inc!udes zero-point energy.
* SUppOitd in part by a research grant from the Robert A. In the previous references, the tot4 energy wns defined t-c!-
Welch Foundation of Houston, Texas. ative to the fround state. The total energy used here is
l *
Alfred ?. Sloan Foundation FeUow. jusr below the u’= 1 threshold.

167
 Volume 34, numb& 1 CHEMICAL PHYSiCS LETTERS 1 July 197.5

specific prior distribution; portions of phase space

with low rotational energies are ‘,‘crowded”.
A local measure (at each gRV)of the deviation be-
tween the post 2nd prior distributions is provided by
the rotational strrprisal

IR(&,) = --In Cp(,“lE,)lp3v’lE,,)}. (3)

The surprisal is plotted in the upper panel in fg. 1.
Amazingly, the surprisal is linear ingR,! The variation
of the surprisai with rotationai level (specified by
gRG)is muc!l simpler than the variations in the sepa-
I rate populations=. It should be emphasized that noth-
I ing was done to “force” the linearity in the surprisal
7
__---e-----L_______ plot. A linear rotational surprisal is certainly not de-
manded in general by quantum mechanics. The re-
sults are the fin21 step m a long road from Coulomb’s
law via the SchrEdinger equation to the reaction cross
----- _-(/ sections, the rotational distribution of the products,
Q
and the surprisal as a function of rotational energy.
- R’
In summary, a very good tit to the surprisal p!ot
Fig. i. Lower panel shows the normalized prior (dashed line) is thus provided by the linear equations IR (gRV)=
and actual [solid line) rotational distributions for !he hydro- 00 +0~g~,, where the slope is 0, = i8.9, and 80 =
gcn exchange reaction at 0.80 eV total energy. The upper -1.7. This implies that the actual and prior distribu-
panel shows the rotational surprisal as a function of the frac-
tions are related by
tion of available energy in each particuhr product rotational
level (determined by S on the top axis). WIEr) =P”(JlE,) exp(-8RgR,) exp(-Bo), (4)
p&ET,). Since pT(ET,) 0; kJV, where xi, is the exit where we note that exp(BO) plays the ro!e of a parti.
cl12nael wavenumber (kJa = (:2@T,/A2)1/2), we ob- tion function [l] _ It is irteresting that the nonequi-
tain the (conditional) prior probability librium rotational distribution can be represented as
the product cf a statistical factor (which is indepen-
PO(J’lE,,)a (2/‘+ l)k,,. (1) dent of dynamics) times 2 dynamic factor (which is
The normalized prior probability distribution is plot- independent of statistics). Similar results are obtained
ted as a function of gR, in the lower panel of fig. 1. at other energies++, with nearly the same OR.
For this distribution, the (pointwise) average value of
gRl is 0.396, and the most probable value is l/2. Also ’ Note that the 0 -S (even) reactive processes are nor ex-
perimentiily’distinguishablc from the corresponding non-
shown for comparison is the normalized ccrz~l rota- reactive transitions.
tional distribution as obtained from one column of ** One might have expecred a Boltzmann Factor exp(-ER,/
the S-matrix computed for the process: kT*) to appear in eq. (4). (Why be surprised by it?) There
itj are several reasons why wa shouid not expect the cnnmriml
ensemble to be the appropriate referent distribution. The
(2) canonical distribution i&derived by atlowing free energy
exch:mpe between the system and a heat bath, with the
where S[JLv,J,L, is an S matrix element at total angular oreruge enargy for an ensemble of systems fixed by rclec-
momcntumj. The narrow actua! distribution is skewed tion of the beth temperature T’. The rotational distribu-
iion produced in a reaction at energy E does not satisfy
toward cold rotational energies* relative to the non-
these conditions. Also, Boltzmxm factors with non-neca-
tive temperatures ;LTeincapable of describing population
e A cold-rotational distribution is aLsopredicted by ctitical inversion:Fix+lly we note that 8~ = constant over thepost
mecfrxAcs air the Porter-Karplus Ha surface; see fig. IOof threshold energy re_sion (OR is energy transferable) while
ref. [ 111 . Our translational energy is 1 .X7 velocity units in T* = (E-Ev)/(ke~) islinear inE (i.e., it is not energy
this fiiiue. trulsferable).
VoIume 34, number 1 CHEMICAL PHYSICS LETTERS 1 July 1975

Table 1 The simple structure of the surprisal plot certain-

Energy dependence of information theory parameters for ly supports the use of the microcanonical ensembie
rotational excitation in the hydrogen exchange reaction
in providing a reference point [I 21 in terms of which
Total energy 0.70 eV 0.80 eV
to analyze the actual product distribution. The re-
Translational energy 0.427 eV 0.527 eV sults reported here do not suffer from dynamical er-
rors generated by use of Iiamilton’s equations for
OR 8.9 5.9 studying the dynamics, nor is there the uncertainty
00 -1.79 -1.72 of knowing if the nascent excited experimental rota-
@,,, 0.101 0.094
tionai distribution has been prevented from relaxing
Zqflu] 1.74 eu 1.75 eu
before the population measurements. The informa-
tion theoretic approach has provided a simple fit to
In contrast to the local measure of the deviation the ab initio computed rotational distribution. This
between P and PO provided by the surprisal, the en- type of analysis should be very useful in prediction
tropy deficiency of the product rotational distribu- and analysis at other energies.
tion provides a global measure (over all gRI) of the
extent to which phase space is not ftiled democratical- I am grateful to Professors R.B. Bernstein and
ly. The rotational entropy deficiency of the actual R.D. Levine for stimulating discussions, and for their
distribution compared to the (maximal entrupy) mi- comments on the original manuscript.
crocanonical distribution is given by the negative of
the average of the surprisal over the actual distribu-
tion References

111 R.B. Bernsrein and R.D. Levine, in: Advances in atomic

and molecular physics, Vol. II, ed. D.R. Bates (Audem-
ic Press, New York, 1975).

or, using the linear equation for i’R,
aS[Jiu] = -R [O, i-0, (g,,)] ,
(6)
where the (point-wise) average value ofgR, for the ac-
tual product distribution is (gR’) = 0.094. (We note
in passing that a large entropy deficiency and a large
positive value of OR follow from a small value for
(gR,)$ ,) From the value of 00 and ~9,) we obtain
ds[JlIJ] = 1.75 cu. This is quite a lafg,e entropy de-
ficiency for a rotational distribution%?. Table 1 il-
lustrates the insensitivity of BR, Bo, and AS [Jlu] to
variation in the total eneru.
* See figs. 28 and 29 in ref. [ 11,
fz III ref. 171, the implication of P = p for the rotational
distribution (zero rotational entropy deficiency) \yns es-
amincd. In ref. i6], analysis of experimental data for the
Cl + HI reaction pave 8~ - I and ~S[Jluj = 9.5 eu. But for
F+HD, kirly large rotational entropy deficiencies have
been extracted from experiments and from classical trajcc-
tories (sc ret [4]).
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to be published.
[91 A.C. Yates and W.A. Lcstsr, Chem. Phys. Letters 24
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B. Liu, J. Chem. Phys. 58 (1973) 1925.
[lOI R.C. Tolmnn, The principles of statistical rnxhanics
(Oxford Univ. Press. London, 1938) p. 57.
1111 41. Ka~plus, in: Molecular beams and reaction kinerics,
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