Doklady Physical Chemistry, Vol. 393, Nos. 4–6, 2003, pp. 339–342.
Translated from Doklady Akademii Nauk, Vol. 393, No. 4, 2003, pp. 511–514.
Original Russian Text Copyright © 2003 by Shestakov.
PHYSICAL
CHEMISTRY
Quantum-Chemical Verification of the Polanyi–Semenov
Generalized Relationship
A. F. Shestakov
Presented by Academician A.E. Shilov July 23, 2003
Received July 23, 2003
Correlation rules play an important part in theoreti-
cal chemistry. Among them, of particular value are cor-
relations that predict rate constants of chemical reac-
tions, which are sometimes hard to determine experi-
mentally. One of the first formulas of this kind is the
Polanyi–Semenov rule [1],
E a = A + α∆H, (1)
which relates the activation energy of an exchange rad-
ical reaction Ea to its enthalpy ∆H. Fixed values of A
and α prevent adequate description of a group of reac-
tions with a wide range of ∆H [2]. The authors of the
rule were aware of this fact and considered the rule to
be a first approximation. The physical meaning of Eq.
(1) is evident. This equation follows from the linear
“buildup” of the heat of reaction along the reaction
coordinate if the transition state (TS) for a thermoneu-
tral reaction with the activation energy Ä is located at
point α (provided that the total change in the reaction
coordinate is 1) and the displacement of the TS for reac-
tions with ∆H ≠ 0 is negligible.
It is the last assumption that deteriorates the accu-
racy of Eq. (1), and it can be discarded taking into account
that, in the vicinity of the TS (r ≈ α), the energy of the sys-
tem changes as the square of the reaction coordinate r:
W
E ( r ) = A + r∆H – ----- ( r – α ) ,
2
(2)
2 Denisov [2, 3] for a group of reactions including sym-
where the coefficient W determines the steepness of the
activation barrier for a thermoneutral reaction. From
dE ( r )
the condition --------------- , it evidently follows that the acti-
dr = 0
vation energy changes as the square of ∆H,
∆H
2
E a = A + α∆H + ----------, (3)
2W
and that ∆H impacts the position of the TS rTS,
∆H
q TS = α + -------- ,
W reactions. Modern quantum-chemical methods predict,
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that is, an increase in the heat of reaction results in ear-
lier TSs, while its decrease leads to later TSs.
In this work, we show that the system energy calcu-
lated as a function of the reduced reaction coordinate by
quantum-chemical methods does depend linearly on
∆H in the vicinity of the TS in conformity with Eq. (2),
as exemplified by radical hydrogen abstraction reac-
tions of the same type.
The accuracy of the Polanyi–Semenov generalized
equation (3) evidently increases if it is applied to a
group of related reactions. If they also include symmet-
ric reactions, for example,
AH + A A + HA ,
the corresponding TS is, as a rule, also symmetric.
Hence, α = 1/2 and relationship (3) takes the two-
parameter form
1 ∆H
2
E a = A + --- ∆H + ----------. (4)
2 2W
Thus, in terms of the linear correlation rule (1), α
should be taken as α < 1/2 for exothermal reactions and
α > 1/2 for endothermal reactions. This corresponds to
the choice of α = 1/4 and α = 3/4 [1] for these two
cases.
The model of intersecting parabolas developed by
metric reactions leads to the analogous expression
B ∆H ∆H
2
E a = --- + -------- + ---------- (5)
4 2 4B
with one parameter B. Experience of using this expres-
sion for processing experimental kinetic data shows
that rather large classes of related hydrogen abstraction
reactions do exist for which Eq. (5) allows one to deter-
mine, to a high accuracy, the activation energy of a
reaction from its heat [3].
Let us verify the validity of expansion (2) for similar
to a high accuracy, the energy profile along the reaction
coordinate
AH + B A + HB;
340 SHESTAKOV

rAH
A + HB
E, au
–158.965

–158.970

–158.975 0
–158.980
TS
–158.985 2.0 fa
1 1.8
–158.990 1.6
2.0 0 1.4 rH–C fb AH + B
1.8
rC–H 1.6 1.2 e
rAH 1 φ
1.4
1.2
e
rHB rHB
. .
Fig. 1. Total energy E along the EtH + Et Et + EtH
reaction coordinate as a function of C–H and H–C distances
and its projection onto the plane passing through the 0–1 Fig. 2. Schematics of projection of the reaction coordinate
line. as a function of rAç and rçB onto the 0–1 line.

the latter is routinely determined by steepest descent
paths in mass-weighted coordinates. However, it is a
priori evident that the overall length of this coordinate
is determined by the features of long-range interaction
of the reagents (e.g., by the structure of pre- and postre-
action van der Waals complexes), which are only indi-
rectly related to the behavior of the system in the vicin-
ity of the TS. For this purpose, we consider first the
reaction coordinate as a function of the length of the
broken AH bond (rAH) and the length of the forming BH
bond (rBH). As an example, Fig. 1, shows the B3LYP/6-
31G* computation results for the reaction
. .
EtH + Et Et + EtH.
As might be expected, the A–H and B–H distances
change in a rather wide range, from their equilibrium
e e
values r AH and r BH to distances on the order of a van
der Waals contact, so that the relative position of the TS
will primarily respond to the reagent dimensions. Thus,
a transformation of the reaction coordinate should be
found such that its length is on the order of the sum of
the elongations of the broken and forming bonds in the
TS: ∆rAH = r AH – r AH and ∆rBH = r BH – r BH , respec-
# e # e
tively. To reduce the reaction coordinate length, we
choose a projection plane that is tangent at the point of
# #
the TS ( r AH , r HB ) to a cylindrical surface specified by
the reaction coordinate as a function of rAH and rBH
(Figs. 1, 2). Then, the line of intersection of this plane
with the coordinate plane is at an angle ϕ to the rBH axis
e e
and intersects the lines rAH = r AH and rHB = r HB at
points 0 and 1. It is easily seen that the corresponding
coordinates are
0 : ( r HB , r AH + ∆rHB tan ϕ ),
e #
1: ( r HB + ∆r AH cot ϕ, r AB ) ,
# e
∆r AH ∆r HB
- + ------------ ,
and the distance between points 0 and 1, -----------
sin ϕ cos ϕ
is comparable with the sum of the bond elongations
∆rAH + ∆rBH.
Thus, to complete the transformation of the reaction
coordinate, the energy as a function of the position of
the point in the 0–1 segment should be determined.
The correspondence between the points of the AH +
B–TS–A + HB curve and the 0–1 segment (Fig. 2) can
be rationally established by using two foci, fa and fb,
formed by the intersections of the line normal to the 0–1
e
segment at the TS point with the lines rHB = r HB and
e
rAH = r AH , respectively. (For a symmetric reaction, fa
and fb are evidently coincident.) The initial portion of
the section of the energy along the reaction coordinate
from A + HB to the TS is projected onto the 0–TS seg-
ment with the use of focus fa, and the final portion is
projected onto the TS–1 segment with the use of focus
fb. For this mode of projection, the resulting plot of the
energy versus the rectilinear reaction coordinate has
second-order tangency at the TS point to the original

DOKLADY PHYSICAL CHEMISTRY Vol. 393 Nos. 4–6 2003

 QUANTUM-CHEMICAL VERIFICATION 341

curvilinear dependence.1 The dependence of energy on E(r) – E0 – ∆Hr, au

the new reaction coordinate is shown in Fig. 1. 0.030 1
This approach was used for analyzing similar reac- 2
. . 0.025
3
tions of hydrogen abstraction by Me and Et radicals
from primary, secondary, and ternary C–H bonds in 0.020 4
alkanes. The initial reaction coordinates were calcu-
lated with the 6-31G* basis set (the Gaussian 98 pro-
gram package [4]) by the density functional theory 0.015
B3LYP method, which recommended itself even in
complicated cases [5]. Figure 3 shows the projected 0.010
sections of the potential energy surface along the reac-
tion coordinate minus the initial energy E0 and the lin- 0.005
ear buildup of enthalpy ∆Hr along the new dimension-
less reaction coordinate r. The r value is 0 and 1 at 0
points 0 and 1, respectively. Figure 3 shows that the 0 0.2 0.4 0.6 0.8 1.0
maxima of all curves are in the same range of r from 0.5 r
to 0.556 and the maximum energies differ by no more
than 0.00058 au ≈ 0.4 kcal/mol. Inasmuch as the heats
of these reactions are as large as 0.010 au and the posi- Fig. 3. Variation of the modified energy E(r)–E0–∆Hr along
tion of the maximum changes from 0.5 to 0.61, it is the dimensionless reaction coordinate r for the reactions (1)
. . .
clear that functional expression (2) is fulfilled well for EtH + Me , (2) i-PrH + Me , (3) t-BuH + Me , and
the family of like reactions. Strictly speaking, this .
(4) EtH + Et .
result means that basic Eq. (3) should be used for cal-
culating the classical energy barrier of a reaction from
the classical heat of this reaction; i.e., to pass to the the reaction coordinate is determined by the force con-
experimentally observed quantities, corrections should stant k:
be applied for the differences in zero-point vibrational
energies between the initial, transition, and final states. k 2 2 k 2
E ( q ) = f ( x ) – --- s n ≡ f ( x ) – --- s .
# #

In summary, let us find the relationship between the 2 2

energy factor W and the characteristics of the TS. To do With regard to the projection of the steepest descent
this, we represent the change in energy in the vicinity of path n onto the 0–1 segment, this expression as a func-
the TS x# as f(x# + sn), where s is the shift along the tion of the dimensionless coordinate r takes the form
reaction coordinate and the normalized vector n speci-
fies a normal vibration with an imaginary frequency, k ∆r AH ∆r HB  2
E = f ( x ) + ---  -----------
#
and explicitly separate the n and x# components - + ------------
referred to the a, h, and b atoms involved in the bond 2  sin ϕ cos ϕ
redistribution in the TS: (6)
(q – α)
2
× ------------------------------------------------------------------------------
-,
[ n ah ( n a – n h ) ] + [ n hb ( n h – n b ) ]
2 2
n = { n a, n h, n b, … } x = { x a, x h, x b, … }.
# # # #
and
Then, it can easily be shown that the angle ϕ is uniquely ∆r HB
determined by the mode of vibration with an imaginary where α = -----------------------------------------
- . Thus, with regard to
∆r AH + ∆r HB cot ϕ
frequency and by the geometry of the TS:
Eq. (6),
n ah ( n a – n h )
#
tan ϕ = – ---------------------------- 1
W = k ( ∆r AH + ∆r HB tan ϕ ) -----------------------------------
2
-, -.
n hb ( n h – n b )
# 2
[ n ah ( n a – n h ) ]
#

In the special case of a symmetric reaction, tan ϕ = 1

# #
where n ah and n hb are the normalized vectors in the
direction of, respectively, the a–h and h–b bonds in the and, under the assumption that the light atom h mainly
TS. The change in energy in the vicinity of the TS along moves in the direction of the a–h bond,

W ≈ k ( ∆r AH + ∆r HB ) ,
1 2
A more complicated mode of projection exists, in which the
direction of projection is specified by two points concertedly
moving from 0 to 1 and from fa to fb. The behavior of the section i.e., W is determined by the product of the modulus of
in the vicinity of the TS, which is the most important for us,
thereby changes slightly, but higher derivatives of the energy the force constant for the vibration with an imaginary
function with respect to the reduced reaction coordinate at the TS frequency by the square of the overall elongation of the
point become continuous. A–H and H–B bonds in the TS.

DOKLADY PHYSICAL CHEMISTRY Vol. 393 Nos. 4–6 2003

342 SHESTAKOV

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DOKLADY PHYSICAL CHEMISTRY Vol. 393 Nos. 4–6 2003