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M F Suárez
*
−E
Z AB =π d 2 v N A N B 2
Z AB =π d v N A N B e kT
*
−E
2 kT
K th T =π d ve K exp T
A potential energy surface for a direct unimolecular reaction without a saddle
point. The surface corresponds to a reaction like H2O → H + OH for dissociation
along a fixed bond angle, where only two internuclear coordinates are required
in order to specify the configuration.
A potential energy surface for a direct bimolecular reaction. The surface corresponds to a
reaction like D+H − H → D − H+H at a fixed approach angle, say in a collinear configuration
specified by the D–H and H–H distances. These distances are measured along the two
perpendicular axes. (Note that in this figure all energies above a fixed cut-off value Emax
have been replaced by Emax.)
Chemical Kinetics
Video
TS
−Δ U (0)
TS (q q ' ) ̊
A
A+B AB → Product [ ABTS ]=[ A][ B] v , RC total −RC AB e k T
q A qB
B
TS
−Δ U (0)
dP Tk q ' ̊
A
=ν ' [ ABTS ]=ν ' [ A][ B] B total − RC , AB e k T B
dt h ν0 q A qB
TS
̊ −ΔkU T (0)
Tk B q ' AB A
K (T )= e B
h qA qB
43 A.
Wassermann, Monatsch. Chem., 83, 543 (1952).
44 A.
U. Blackham and N. L. Eatough, J. Am. Chem. Soc., 84, 2922
(1962).
Comparison of Arrhenius activation
energies (Ea ≡ Earrhenius) calculated
via QM (red solid lines), ICVT (dashed
black lines), and ICVT/LAG (solid
black lines) for the reactions of 4.1 H
and 0.11H with H2 as a function of
temperature (T ).
2a
Particle Mass l (Å)
(a.m.u)
e- 1/1750 26,9
h
H 1 0,63 =
mv
D 2 0,45
C 12 0,18
Br 80 0,07
l: De Broglie wavelength
kinetic energy = 20kJ/mol m: mass
v: velocity
Consequences of Tunneling
on Reaction Kinetics
R.P. Bell developed a quantum tunneling correction factor, Q, and explored its
effect on an Arrhenius treatment of reaction kinetics
−Δ U eα
K (T )=QAexp (
RT ) Q=
β−α
−α −β
[β e −α e ]
1/2
ΔU 2 (2m ΔU )
α= β=2a π
RT h
Temp ( ̊C) kH / kD
-30 17
-100 53
-150 260
In organic reactions, this proton tunneling effect has been observed in
such reactions as the deprotonation and iodination of nitropropane with
hindered pyridine base with a reported KIE of 25 at 25 °C:
Edward Sheldon Lewis and Lance Funderburk (1967). "Rates and isotope effects in the proton transfers from 2-
nitropropane to pyridine bases". J. Am. Chem. Soc. 89 (10): 2322–2327. doi:10.1021/ja00986a013.
Reaction of HO with CO:
Tunneling Is Indeed Important
Following ILET by Polarization Anisotropy: Femtosecond polarization anisotropy methods are used to
follow the hopping of the electron from ligand-to-ligand (i.e. interligand electron transfer or ILET) that
takes place in the metal-to-ligand charge transfer (MLCT) excited states of two Os(II) dyes. Adiabatic
ILET in the Os(bpy)32+ complex occurs with an 8 ps hopping time in acetonitrile.
J. Am. Chem. SOC.,
Vol. 106, No. 10, 1984
Intramolecular electron-transfer
rate constants as a function
of free energy change in MTHF
solution at 296 K. Electrons
transferred from biphenyl ions to
the eight different acceptor
groups, A (shown labeling the
points), in eight bifunctional
molecules having the general
structure shown in the center of
the figure.
Curva de energía libre diabática para una reacción de
transferencia de carga asimétrica.
1 1
V R ( qc )=V P ( qc ) f (q c −q R,0 )2 =∆ G 0 + f (q c −q P ,0 )2
2 2
∆ G0 1 1
qc = + (q P ,0 +q R,0 ) ∆ G ‡= f (q c −q R ,0 )2
f (q P ,0 −q R ,0 ) 2 2
2
1 ( ∆ G 0+ λ )
λ= f (q P ,0−q R ,0 )2 ∆ G ‡=
2 4λ
{ }{ }
2
1 1 1 1 1
( )
0
−( ∆G + λ ) λ 0= ( Δe )
2
+ − −
k ET = A Arrhenius exp 2 a1 2 a2 R ϵ ∞ ε0
4 λ kBT
0 2 2
( ∆G + λ ) =(−eη+ λ ) =W
dW
W ≈ W ( η=0 ) +
dη ( ) η=0
2
( η−0 ) =λ −2 λeη
−λ 2 −2 λe η
(
k ET = AArrhenius exp
4 λ k BT ) (
= A Arrhenius exp
−λ−2 eη
4k BT )
eη
k ET =k exp
0
2 kBT (
=k ox
)
Electron flow through proteins and protein assemblies in
the respiratory and photosynthetic machinery commonly
occurs between redox active cofactors that are
separated by large molecular distances, often on the
order of 10–25 Å. Although these cofactors are weakly
coupled electronically, the reactions are remarkably rapid
and specific. Understanding the underlying physics and
chemistry of these distant electron transfer processes
has been an overarching goal of theorists and
experimentalists for many years.
−√8m r Δ E
k ∝exp( )
ℏ
Angew. Chem. Int. Ed.2013,52,1–5
Collision between two spheres:
Laura Pedraza-González, Johan F. Galindo, Ronald González, and Andrés Reyes* Departamento de Quıımica, Universidad Nacional de
Colombia, Av. Cra 30 # 45-03, Bogotá, ColombiaJ. Phys. Chem. A, 2016, 120 (42), pp 8360–8368DOI: 10.1021/acs.jpca.6b06517Publication
Date (Web): October 9, 2016
Diels-Alder Reactions
J.Org.Chem.2014, 79, 8968−8976
Phys. Chem. Chem. Phys., 2016,18, 31895-31903