Interacción con luz: fuente de energía y de información

bacterias con preferencia clara por colores específicos

El espectro solar: entre 250 y 1250 nm nos llegan ~1000 W/m2
 Lo aprovechan directamente los organismos fotosintéticos.
Chlorobium Halobacterium Synechoccus Spirogyra Euglena

Volvox Wolffia Elysia chlorotica

absorción de un fotónà transferencia y separación de carga à
reducción de dioxido de carbono
 Las bacterias fotosintéticas tienen mucha membrana y carboxisomas.

~10 veces lo que

tiene E. coli de
membrana

Prochlorococcus Halothiobacillus

Synechocystis ~10 carboxisomas/bacteria

En promedio hay 250 Rubisco por cada carboxisoma.
Rubisco es la proteína más abundante del planeta.
La repartición de carboxisomas en la bipartición es activa.
Synechococcus
Confinement Energies of Electrons
(p.
photons 190),andwe the showed
wavelength the confluence
λ of In Figure 5.1
of energythrough
scales relevant
nt Energies of Electrons Inthe light
Figure related
5.1 180
e toshowed the confluence of energyOne scales relevant

photon energy (kBT )

but important
many relation
biological processes. of the lines shown in 160
that
he La luz es
confluence
ological
una
processes.
colección
of energy
One of the
de fotones.
scales
linesrelevant
shown in that 140
figure
ocesses. corresponds to the energy of quantum mechanical con-
sponds toOne of the of lines
hcquantumshown in that con-

ESTIMATE
the energy mechanical 120
finement as a function λ = of , the length scale of the (18.1) confining box.

ESTIMATE
the energyofofthe
a function quantum
lengthEscale mechanical con- box.
of the confining 100

ESTIMATE
In particular, the idea is that the act of confining a quantum 80
of
ar, the
the length
idea is
La fotosíntesis
Planck’s constant
scale
that the
seand
debeof the
act ofconfining
c aislathe
confining
interacción
speed
abox.
quantum
ofdelight. Thea conse-
ch particle
as an such as
electron toan a electron
box implies to aa certain
box implies
energy certain energy
60
isfotones
thisthat
simplethe
con actelectrones
of confining
relationship are a quantum
shown
confinados inengraphical formwayin to esti-
40
cost
epends that
upon depends
the size upon
of thatthebox.size of
One that
way box.
to One
esti-
ctron
Our to aenergy
attention
moléculas.
mate the
boxis implies
focused
scale of
a
on certain energy
the wavelengths
confinement is to around Heisenberg’s
exploit the 20
ergy scale of confinement is to exploit Heisenberg’s 0
nof the
the size of
spectrum,
uncertainty relationthat box.
since One
these areway
the to esti-
most relevant to the
relation 250 5
etic processes
of confinement of
Confinar electrones interest
is to cuesta here, as
exploitenergía, is clear
Heisenberg’s
más from Figure 18.2.
photon
idea is not only useful for thinking
"p"x ≈ !,
, la caja.
≈ !sea about the energy
(18.2) asso- (18.2)
mientras más "p"x pequeña
photons of different wavelength, but also provides the Figure 18.8: Re
ntroduce
where
imple "p"x we !, of .the
h/2π
≈introduce
estimate
!= The !idea of
= h/2π
energy ofHeisenberg’s
. The idea
electrons (18.2)
that princi-
of Heisenberg’s
are confined princi-
and wavelength
he
th uncertainties
molecular
ple is that the in the momentum
dimensions.
uncertainties Treating
in theand positionas
molecules
momentum areelectron
and position are
Si
ndent. se confina en
inIf. precisely
the
Theelectron
una caja de tamaño
=ered
h/2π
not independent.ideathe Ifissame
of confined
spirittoof
Heisenberg’s
the electron aisregion
princi-
confined of size
simplification to aasregion
the of size
ycan ∆xsolve
= a, formodels
simplified the solve
corresponding
discussed uncertainty
throughout in the
nties
"x =ina, the
we momentum
can forandthe position
corresponding arethe book and
uncertainty in the
s, momentum,
e
resulting
understand
electron
in the
is the
energy
relation
resulting
confined
estimate
inbetween
to the
a energy
region molecular
size dimensions
ofestimate
ion wavelength. 2
or the corresponding p !uncertainty
2
2 in2 the
E= ≈ . p ! (18.3)
n the energy estimate 2m 2maE2 = ≈ 2
. (18.3)
Confinement Energies of Electrons 2m 2maIn Figure 5.1
es resulting
e showed 2 the from 2 this simple
confluence estimate
of energy as a function
scales relevant
The penergies ! resulting from this simple estimate as a function
Eare
= shown
ological ≈ in Figure
processes. 2
. One 18.9.
of Thislines
the simple (18.3)
shownresultin and
that
t Einsteinwould,
nevereven
accepted
when the
detector
electron theelectrons
funda-
a complex number,
are arrivinggun which
only one is wh
In fact, this is nothingp
a
ys in quantum
Los about
describe the
(not
mechanics,
electrones probability
se explain!)
detector
portan asofthe
thisondas
state
famously
como finding
square
y of the
affairs,
como that ofwe
he quantum
its associate
used
partículas. modulus, pa
to confirm w
su
lar
the two position.
trajectories Unlike
that the conjugate
xthe amplitude
electron of ψ. ofMore
xwavelength.
can take,a precisel
classical
passing
What th
n
is unus
y dice with the universe!” (Born
(B) & xt the
x at time quantum
classical notionsparticle
of partfu
(B) or through slit 2,
amplitude probability
itself has no amplitudes
simple physical and ψ2 (x
ψ1 (x) meaning
can thus they the
use (B)
are emitted
wave by thesle
functio
ability of detecting the electron
a complex number, which is why at position
amplitud de x if
the probability slit
!
probabilidad
" 2
# (
sl
individual particles, sho
s the same
is Prole
1 (x) =in
|ψquantum
(x)|2 (P (x)mechan-
= |ψ (x)|2 ). Now,
particle’s position,
as the square of its modulus, |ψ| = ψ ψ, wher
1 2 2 in
would, 2 the = xthe
case
"x∗when
even
2 −
whe p
e
sical wave, such as a water
conjugate of ψ. wave,
in thea usual
More precisely,
way
describe
! |ψ(x,
thatexplain!)
(not
t)|
exploits
2 dx is d
th
2 : ⟨. . .⟩the ∞ trajectories2thatg
two
ic wave traveling through a medium, |ψ(x)| = −∞ (. . .)|ψ(x)| dx.
D LIFE at time t the quantum particle is located
or through slit 2, betw
probab w
the case ofcana classical
thus use the wave, wave the ability of detecting there
function to compute th
!" # is P1 (x) 2
= |ψ1 (x)| (P2 (x) P=
wave at a particular
particle’s position
position, "x in =the x2 − ⟨x⟩2 , where the av an
probabilidad de encontrar p
y of the disturbance described byANDthe
in the726usual way
Chapter that
18 LIGHT exploits
LIFE the probability
al electrón en x si la co
while for a quantum
|ψ(x)|2 : ⟨. wave
! it (.tells
∞
. .⟩ = “chap18.tex”
. us 2 dx.rendija 2 está tapada th
.)|ψ(x)|
−∞ — page 727[#11]
the quantum particle at that particu- at
st
e of a classical wave, —the
“chap18.tex” pageprobability
726[#10]
im
hysical
open, the meaning,
resultingand in factamplitude
probability it can beis ψ12are (x) open,
= ψ1 (x) the resultin
+ ψ2 (x) 1
e open, the resulting probability amplitude is ψ12 (x) and= ψthe
1 (x)2 .associated
+ ψ2 (x) Ap
dthe theprobability is actually
associated probability iscomputed
P12 (x) = |ψ1 (x) + ψ2 (x)| Notably,
d 2the associated probability is P12 (x) = |ψ 1 (x) + ψP212 (x)2 .̸= Notably,
(x)| P1 (x) + P2 (x) Fe
a
(x) ̸=
ψ| =Pψ ∗
1 (x) 2 (x) as would
ψ,+ Pwhere ψ is be
∗ the expected
complex for classical
which particles,
each detected for A
2 (x) ̸= P1 (x) + P2 (x) as would be expected for classical particles, for
ich each detected
2 dx is electrondeisqueassumed to t have reached thex ydetec- To
hich|ψ(x,
eacht)| detected the
electron probability
probabilidad is
“chap18.tex” — page 727[#11] assumed that
to
en el tiempo have tor esté
reached
la partícula following
the
entre ax+dx
detec- defini
1
following a definite trajectory that took it either through
or through slitslit 1 f
2. In
hat namely,
has zero uncertainty equation (albeit one with complex coefficients) ∂ψ(x, t) for the wav
Schrödinger Equation in its momentum. i! = Ĥψ(x, t)
the observable quantities namely, La ecuación
representedUsing de
by
the Schrödinger
operators,
Hamiltonian we will
operator defined
∂t in Equation
∂ψ(x, t) !2 ∂ 2 ψ(x, t)
st directly
Las
The of on
thethe
distribuciones
job ienergy. The
= −energy
!de probabilidad
governing equation the ofSchrödinger
asociadas is represented
quantuma las equation
funciones
+ U(x)ψ(x,
mechanics t).dein
by an a to
onda
is more
(quecompact
predict representan
(18.7) form
2m 2 2 ∂ 2 ψ(x, t)
known as permiten
estados)
the the Hamiltonian.
probability
∂t
determinar
amplitude For a
promedios
associated
∂x
particle
∂ψ(x,
de
with t)
moving
cualquier
a quantum !variable
in a particle
one- dinámica, descritat).consa
atU(x)ψ(x,
time
The eigenfunctions
i! =− of the Hamiltonian
+
nal energy landscape characterized by ata
∂tpotential 2m U(x),∂x 2 lost)operadores dan
∂ψ(x,
we
given
t un that
operador. we
Las know the Eψ
funciones amplitude
de onda
, que
which son some
when earlier
eigenfunciones
substituted time.
i ! de Such
into an
= Ĥψ(x,
the t).
Schröd
theUsing the
Hamiltonian Hamiltonian
as operator E defined in Equation 18.6, we
∂t can write
equation was first written down by Schrödinger in the form of a rate
valores definidos para las variables dinámicas.
the Schrödinger equation in a more compact form
equation (albeit one Using
!2 ∂the
with 2 Hamiltonian
complex Thecoefficients)
operator for the defined
wave in Equationsatisfy
function, 18.6, w
Ĥ = − + U(x).
eigenfunctions of the
(18.6)
Hamiltonian
∂ψ E (x, t) t
namely, the
2m Schrödinger
∂x2i! ∂ψ(x, Eψt) equation
Hamiltoniano:in a moreoperador icompact
!
E , which when substituted into the Schrödinger
deform = EψE (x, t
energía
= Ĥψ(x, t). ∂t (18.8)
∂t
∂ψ(x, t) !2 ∂ 2 ψ(x, t) ∂ψ(x, t) ∂ψE (x, t)
i! = and
− 2
i!
+ U(x)ψ(x, t). =i! Ĥψ(x, t). (18.7)
= EψE (x, t).
∂t 2m
The eigenfunctions of the Hamiltonian satisfy the equation ĤψE =
∂x ∂t ∂t
EψE , which when substituted into the Schrödinger equation leads to
Using the Hamiltonian
evolución
The operator temporal
eigenfunctions and
defined
dein
oflaEquation
función
the deψonda
Hamiltonian
18.6, t)satisfy the0)e equa−iEt
Ewe(x,can =write
ψE (x,
the Schrödinger equation EψE , whichin ∂ψ (x, t) compact
a more
Ewhen substituted forminto the Schrödinger
29/9/2012 11:27 equation
!
sus eigenfunciones: i ! = Eψ E (x, t). ψ E (x, t) = ψ E (18.9)
(x, 0)e −iEt/
.
∂t
In other
∂ψ(x, t) words,∂ψEthe (x, t)probability amplitude
Lo que dice esta ecuación i! esstate
= Ĥψ(x,
que la t).
iprobabilidad
! definite = Eψ deE (x, (18.8)
encontrar
t). una
and in∂taIn other with
words, the probability
∂t energy evolves
amplitude for sa
partícula en la posición x in
e−iEt/ no! ,a cambia
statetherefore
and withcondefinite
el tiempo,
the energy sievolves
está ensimply
probability ofunfin
−iEt/! , and −iEt/ !
therefore
The eigenfunctions
estado con energía andofdefinida.
the
ψE (x, t)e= ψE (x,
Hamiltonian 0)esatisfy . the the probability
2equation (18.10)
Ĥψ E 2=
of finding t
tion tion x, P(x)
x, P(x)
= =
|ψ|ψ
(x, t)| =
E (x, t)|2 = |ψ (x, |ψ (x, 0)|
E 0)|2 , does , does
not
no
chan
EψE , which when substituted into the Schrödinger equation leads to E E
sense, sense,thethe eigenstates
eigenstates of ofthe the Hamiltonian
Hamiltonian
−iEt/ ! are stat ar
In other words, the probability amplitude ψE (x,for E (x, 0)e
t) =aψquantum .
particle
Los ∂ψSchrödinger
(x, Schrödinger
t) equation.
equation. They
They are are referred
referred to as theto a
in aestados
state withestacionarios
definite
i!
Ede la ecuación
energy = evolves
Eψ (x, t). de
simplySchrödinger
by a phaseson
E particle. The fact that energy levels of el
los
factor
(18.9) niveles
! quantum
∂t quantum particle. The fact thatatenergy level
e energía
de−iEt/ , andde therefore
la In the
partícula.
other probability
words, the of finding
probability the particle
amplitude posi-
a finite region of space are quantizedfor a quantu
is what leads
2 a finite region
2 of
tion x, P(x) = |ψE (x, t)| = |ψE (x, 0)| , does not change in time. In thisspace are quantized is wha
 finite-well problem, we solve the Schrödinger equation
inspection reveals region thatisthisgivenis theby same equation
which will that arises
restrict the setin of allowed energi
ct
onregions.
reveals For
that
El modelo the
this two
is
thatofthe the
de regions
same
laelectron where
equation
partícula en thethat
una potential
ka
arises
caja to de= invan-
nπ .
tamaño a: orbitales
out the dynamics a spring (thatbe is,
crete
confined
the harmonic
values.
a one-dimensional
oscillator), box of lengt
ödinger equation
dynamics of a spring can be imposed
(that written in
is, the harmonic thecondition
same wayThe
oscillator), as we first of these conditions
solution can bewe writtenhave by inspection the as !2!d2 ψ(x) (see the edges of the solution
canen
viousbeuna zonaby
problem,
Invoking
written con
namely,
Figure Vthe
inspection
18.11(A))=as0 The second
0(x)definition k−= 2mE/ condition
2
2
!= ,Eψ(x).leads
we seeusthatto thethese realiza
(18s
2m dx
imply 2ψ(x) 2corresponding
= A cos kx + B sin energy
kx, eigenvalues (18.12)
ψ(x) − ! d ψ(x)
= A cos kx + B=sin kx, como ψ(0) (18.12)
= ψ(a) = 0, ka = nπ. (18
! dx2Cursory Eψ(x).
inspection reveals that (18.16)
this is the same equation that arise
2m 2 2 " nπ
! the(that # 2 !
we define
! k = 2mE/ working ! . outVerification
the dynamics that of this is
a spring solution
is, the harmonic 2oscillat
k = 2mE/ ! 2 . which
Verificationwill restrict
that Invoking
the
this isset E
theof the
allowed
solution
=
nplugging definition
energies , k to = a 2mE/
special ! ,setweof
simply
where theby differentiating
potential andisthe solution
nonzero, ψ(x)the twice
can beandwritten
Schrödinger by back
inspection
equation
2m a energyinto as
by differentiating
ation. crete ψ(x) values.
twice The
and imply
first
plugging of corresponding
these
back conditions
into forceseigenvalues
us to adopt A
as
f ¿y
thesi deepest
laswhich,
paredes The nosecond
aside
results sonabout condition
del
from altura leads
infinita?
numerical
both =us
classical
ψ(x) Se to
Afactors,
cos the
desparrama
andkx + realization
B is
quantum la that de
kx,función
sinprecisely theonda.
same
(18
eepest results
2 2 about both classical and quantum ! 2 " nπ # 2
!
cal problems d
we of found this variety
from= Eψ(x).is
our thesimple
way in which
estimate constraints
. using Enthe
= Heisenber
ψ(x) ! para ,
lems −
of this variety − V
is0 ψ(x)
the way in which la ka
zona
constraints (18.17)
= nπ
donde V0 that
= -5 (18
2mtainty
uantization. 2 where
For example,
dx we define
when k
weresult
= 2mE/
pin a string! 2 . Verification
at its ends, this 2mis thea solut
on. For example, principle.
when we pin Thisa string at will
!
its ends,serve us in our attempt t
e the vibrational follows simply
frequencies by differentiating
to adopt only a2mE/limited
ψ(x) twice
2 , weset see and plugging back i
of
stand
ions, we frequencies Invoking
can recognize the the
connection
the definition
solutions between
which,as k =
aside absorption
exponentials from ! of numerical that
wavelength theseand
factors, solut
is mp
brational
Similarly, in the the to adopt
equation.
quantum only
mechanical a limited
setting, set of
by insisting
imply corresponding
dimensions. we energy
found eigenvalues
from our simple estimate usin
y, in the quantum Onemechanical
of the deepestsetting, by insisting
results about both classical and quant
mechanical κx problems tainty principle.
of this variety2 " nπ
!(18.18) This #2 result
is the way inwill which serve us
constrai
I (x)
ψimply = Ae En = , pin a string at its (18
quantization. stand the
For example, connection
2m
when we
a between absorption enw
Solutions for the
we force the vibrational Box of Finite
dimensions.
Depth Do Not Vanish
frequencies to adopt only a limited set at the Bo
which,
values. aside from in
Similarly, numerical
the quantum factors, is precisely
mechanical the by
setting, same en
insist
ψII (x)we
The found
particle-in-a-box
= Be κ′x
+ Ce from
−κ ′ x ourmodel simpledescribed
estimate
(18.19) using
above
29/9/2012
thecanHeisenberg
11:27
be genera un
the more tainty realistic
principle. case Solutions
This result
in which for
willthe serve
the Box usofin
bounding Finite Depth
our well
attempt isDo toNo
not uni
GHT AND LIFE 29/9/2012 11:27
high,stand the connection between absorption wavelength and molec
resulting in some leakiness. This simple model will
dimensions. The particle-in-a-box model described PHOTOSYNTH abo
the basis of our discussion of the electron transfer proces
the more realistic case in which the bound
#14]
photosynthetic reactions. A schematic of the system is show
29/9
 of biological pigments can be sown by appealing to the par
To corresponding
compute these energy number differences,
of electrons. we resort Taking to theourparticle-in-a-
cue from mol
Los a-box problem
pigmentos worked
fotosintéticos out sonin Section
cajas de 18.2.2
electrones. (p. 730). The k
box model
such as already worked
β-carotene out
(see in detail
Figure above,
18.13), save
wethe that
begin now bywe have
thinking
that is the basis of this section is that absorption wavelen
to bepigment
more careful about
molecule the linear dimensions of the molecule and the a
related to thelaofenergyinterest
longitud de as
differenceonda a between
alinear
la quechain of N
the relevant
absorben atoms
molecul
depende de
corresponding
assumethrough number
that the of
mean electrons.
spacing Taking
between our cue
atoms from molecules
along the chain is
the equation
sus niveles de energía: el gap HOMO-LUMO
such as β-carotene (see Figure 18.13), we begin by thinking of the
by a. This means then that the overall length of the chain is (N
pigment molecule of interest as a linear hc chain of N atoms and we
From the standpoint of the quantization = Ealong conditions
2 − E1the . chain worked out f
assume that the mean spacing between atoms λ is given
by a.chain, this implies
This means then that the overall length of the chain is (N − 1)a.
From the standpoint
For example,can supongamos
of thewe quantization
will
accommodate cadenas
often twofirst
suchlineales
conditions
be de
interested
electrons N átomos
worked byin out
thethe separados
for the
minimum
Pauli princi
can accommodate
k(N − 1)a =two nπ. such electrons by the Pau(
chain, this implies
excitation una
to excite
principle distancia
isanboth a; longitud
electron
fundamentalin thetotal =
lowest
and
principle is both fundamental and deep, and he
(N
deep,– 1)a
molecular
and here,energy
instea
to the next unoccupied
these depths, we
these depths,energy
opt forwe state.
merely
opt for This is sometimes
noting
merely that
noting referr
the that
Pauli p
th
visible light

2 2
visible light

We canthe then findus the

HOMO–LUMO thatenergy
k(N − 1)a
forgap,
us
eigenvalues
systems
that with= nπ.
with many
the acronyms
for systems
aselectrons,
with
! k we
E =standing /2m.
many electrons, forTo
(18.34)
fill up dete
thefil
“highe
we
the absorption
pied molecularwavelength
one electron at athat
orbital”
one electrontime
andat corresponds
from
“lowest
a time lowest to exciting
energy
unoccupied
from lowest toenergy
highest
molecularan
to
el
ener
hig
We can thenthe findhighest
the state
energy
ahora eigenvalues
hay
to que as Elastate
encontrar 2 kelectrons,
n!del 2HOMO. ToLo determine
queforimporta
from respectively. occupied
able energy
accommodate
state able to accommodate
=two to
/2m. the
two lowest
one
electrons, unocc
each
one f
s
the absorption
energy state, weIfuse
Towavelength
compute N el
es is número
an even
that
these denumber,
corresponds
If Nenergy
electrones
is an even
the
differences, tohighest
π:
number,
1exciting
porwe occupied
átomo,
the resortan
highest
porstate
doselectron
to is g
orbital
the
occupiedparti
from the highest box model occupied
already energy
worked state
out in to detail
the lowest above,unoccupied
! 2 (N/2) 2save
π 2 that now
energy state, towebe use
more careful about the hc
EN/2dimensions
linear = 2 (N/2)2 π 2
!of the. molecule
energía del HOMO: λ= . 2m EN/2(N =− 1)2 a2 2 2
. (
corresponding number hc of electrons.
#E Taking our 2m (N cue from
− 1) a m
such as Using λ(see
= Figure
this strategy,
β-carotene . we find 18.13),
that we begin by (18.35)
thinkin
To make furthermolecule Using
progress, this
of we
#E strategy,
now need we find
to compute that #E Nitself. H
10 15 20 pigment 25 interest as a linear chain of atoms
0mber5of we10 find 2π 2 +21chain
Nthe
atoms
Tonumber
make of the
further
20 highest
15assume 25that
progress, occupied
the we mean
now energy
spacing
need = to
E
level
between
compute −
and
E atoms
#E its
=
corresponding
!along
itself. How do 2, N
atoms "E (N/2)+1 N/2 !
2 (N − 1)2 π
we do the
find so, highest
wea.need
by This to count
means
occupied then upthat
energy the
levelthepiand electrons
overall
"E = Ecorresponding
its length
(N/2)+1 in−2ma
the
EN/2
of themolecule,
chain
= n? To2 is (
Wavelength of light 2ma (N
 ! π N +1
n as"E
revealed in Figure
= E(N/2)+1 18.13(D).
− EN/2 = , (18.37)
2ma2 (N − 1)2
La longitud de onda de absorción depende del tamaño de la caja.
: Number
the of Incident Photons Per Pigment
wavelength
One of the interesting points about the interplay
light absorption 8mc and electron transfer is the “stoi-
2
2 (N − 1)
λ = In aparticular, . it is interesting to(18.38)
y” of the process.
h N +1

ESTIMATE
e how many times each second a pigment molecule
ed this
of to excitation
analysis by
arean
a = distancia incident
shown photon.18.14, where we see
entreinátomos
Figure
gin,
model weyields
make absorption
the simplifying assumption
of visible light for that all with a
chains
n N = número de átomos
tothe
25 incident lightresult
atoms. This have agrees
the same energy given well
embarrassingly by with
and
ze oftaking λ = 500 nmdouble-bond
the conjugated results in ansystems
energy per
in pho-
chlorophyll
ughly 4 × 10−19 J. We can now use this number to find
nd β-carotene (22 atoms).
¿cúantos
oximate fotones
number llegan ahitting
of photons la superficie
a square meter
l worked out in this section represents2 a vast simpli-
onddeby assuming
la important
Tierra cada that the full 1000 W/m is being
segundo?
e most point to take away from the calcula-
. By dividing this incident power by the energy per
here is the way in which the landscape of confinement
we can find the number of photons, namely,
allowed energy
supongamos 1000levels.
W/m2, yHowever,
λ = 500 nmto really understand
spectral
of E = 4properties
photons
à xper area
10-19 of second
J per a given light-absorbing molecule
ore thorough quantum mechanical treatment that explic-
103 J m−2 s−1 de área 1 nm2, toca
atomic positions as well as theconsiderando
s for the ≈ underlyingpigmentos
wave
n addition, 4we× 10
wouldJ/photon
−19
have to go beyond the simple
de 2500 dis-
fotones/pigmento por segundo
considered 1 here22to account −2
≈ × 10 photons m fors−1 the broadening
(18.39)of the
s revealed 4in Figure 18.13(D). se absorbe 1 de cada 100 que llegan
Se absorbió un fotón … ¿y ahora qué?
hay que almacenar esta energía
separando cargas

usadas en fotosíntesis
En fotosíntesis lo que interesa es separar carga: transferencia de e-
 e particle
E is found outsidethe electron
position the
is setbox,bytransfer
thelength
the process
ξ andand
bidden
uncertainty the the
region
in itsextent to
outside
uncertainty of
in
La transferencia de -
e ocurre
tion is set by the lengthtumelectron transfer
is determined
ξ and the bypor
occurs
uncertainty
tuneleo
depends
to
inthe
Heisenberg’s upon
its momen- the “leakage
considerations
principle andof
tron
≈ ! wave
. For function
the from
particle to the
ing
escape donor
protein
from site
the tobox,
molecules the itac
or
s
is determined by Heisenberg’s
"p /ξ
If the momentum principle
particle donador
is found and
outsideis
ycompensate
aceptor given
deben
thefor by
estar
box, the cerca
uncer
(A) enough to the electron transfer
the pr
differen
≈ !/ξ . For
E the particle toposition
escape is from
set by the
thebox,
lengthit should
ξ and the
electron have
uncertainty
transfer occurs in
d
its energy E aspara measured
escapar from
de lathe
caja,bottom
debe of the
tener b
ugh momentum ª to compensate for the difference
tum is determined by Heisenberg’s
tron between
wave principle
function from and
depth of the potential suficiente well V 0
momento, that is,
para ganarle a ito
nergy E as measured from "p ≈ !the bottom
/ξ . For of the
the particle box
to the
If escape andfrom
particle thethefound
is box,
th of the potential well enough E momentum
V0 , that p 2 to compensate
is, la diferencia 1
! "E
entre
position y for
! 2 is set
V0 the differen
by the leng
V0 its energy E as measured from
ª
≈ tum is the
≈Vbottom
0 − E , ofby
determined theH
! "of
depth 2m 2m V ξ, that is,
2 the potential well 0 !/ξ . For the particle
p2 1 ! "p ≈
p2/2m≈ where we have −E ,2
≈ V0 estimated enough
the (18.40) p bytoitsco
"2momentum
!momentum
2m 2m ξ p 1 energy
its ! EV as measured
"p. From this equation,
ª we arrive at≈the
≈ 0− E,
estimate
(B) 2m 2m
depth of the potential we
ξ
re
01
we
0.1
have1 estimated
10
the momentum p by its uncertainty!
tunneling length (nm)

From this 5 where we have estimated the momentum . p by

p2 its
(eV)equation, we arrive at the estimate 2m(V − E)
ξ ≈ #
well depth
2 "p. From this equation, we arrive0 at the estimate≈
2m
Tunneling length as a 1 !
1 0.01 0.1 1 0.5 10ξ ≈ For
# an electron .in the ground state, whose energy
! (18.41)
well depth. (A) ξ ≈where
# we have. estimated
well depth (eV)
e well showing the 0.2
2m(V
zero, the 0 − E)
tunneling
para length
un can
electrón be
en estimated
su
2m(V0 − E)estado as ξ ≈ 0
base,
"p. From this equation, w
f the wave function into0.1 where V0 is the condepth of the
E cercana well measured in el
a 0:
17: Tunneling length as a
an electron
orbidden region. in
the well depth. (A)
the
(B) The ground
0.001 For an
units.
0.01 state,
This
0.1 whose
electron
dependence
1 energy
in10the ground isstate,
close
of tunneling to energy
#whose
length on c
h is thetunneling
o, distance from zero,
energy the
is tunneling
plotted length
in Figure can
0.2be
as ξ ≈18.17(B). estimated
V0 , as ξ ≈ξ 0≈
of the
the well showing thelength can
well be
depthestimated
(eV) nm/
hich there is an where V0 is the depthin of electron
the well measured in e
ver
re of
V theis
wave function
the depthinto of the well measured volt
0
bability of finding the
 unknown coefficients. H For our purposes here, the key
= −V dx ψA∗ (x)ψ B (x),
Para que ocurra el tuneleo, deben traslapar las funciones
extent to which the wave functions0 de onda.
in the two wells ov
cally, we are interested in how much of wave function ψ
whereinto
V the welldepth
is the B and of
el vicethe
traslape versa.
de This
wells
las asdegree
shown
funciones de of in
overlap
ondaFigu
extent to which the tunneling between the two wells wil
tunneling rate itself
delisdonador
proportional to the square
A y el aceptor B: of
captured in
the form !a
H = −V dx ψA∗ (x)ψ
2 B (x),
rate
0 ∝H ,
where V is the depth of the wells as shown in Figure
and, tunneling
as is shown in the appendix,
la velocidad
rate itself using
es proporcional
is proportional Hof2 this
ourabox
to the square mo
giventhe
here,
formwe find
2
2π ∝ H ,
rate
rate = H 2 F 2 ρe−2κd ,
! using our box model
and, as is shown in the appendix,
given here, we find
where F is a distance-independent
la eficiencia decaenumerical factor
con la distancia
the details of the integral rate
given 2π 2 2 the
= above,
H F ρe−2κdfactor
, ρ wi
!
F es un factor numérico
where F is a distance-independent numerical
ρ es la densidad de estados factor tha
accesibles
the details of the integral givende
κ es la longitud above, the factor ρ will b
decaimiento
La dinámica de la transferencia electrónica, experimentalmente.
cómo saber quién le pasa electrones a quién: PC à APC à Chla
 system
y of a veryCalibración
brief and apulse
(ps)del
laser second to onecell
the to query
culture. it At
as early
reve
efecto de distancia y la eficiencia
e. Over about in1000
chargeps state
(1 ns),ofthe
the copper duespectrum
fluorescence to electron sh
cence intensity atThe
transferencia entre number
the cobre (azul)of acceptors
y rutenio
characteristic (rojo) enthat
wavelengths azurina have
for each rec
o
κ es la pendiente
N
n transfer to eachA , is a function of time and satisfies
pigment and the lifetime of each pigmen the di
ol. 39:233, 1984.)
dNA
= k(N0 − NA ),
dt
where N0 is the total number of proteins
tron transfer
er of molecules rate for
N0 . Using a given donor–accept
Equation 18.48 for N
directly towe write
the as
expression p(t) dt = ke−kt dt, the
a transfer event between times tk and + dt.
= k0 et−2κd ,
hese experimental
la proteína results
se encarga de orientar also demonstrate
a los pigmentos th
y ponerlos a distancias
favorables: ir a where
través de 1/κ is the
la proteína length
es más scale
rápido que over
a través del which
vacío o
hrough
del agua
protein over a given distance is sub
than tunneling decays through
in the classically
water forbidden
or through region.
a va W
number of acceptors that have received an
ated in Figure 18.20(C). That is, the nature of
también ayuda con efectos electrónicos
G* of the two parabolas occu
Combining
oftion
thestate.
two
donorthe result
parabolas
molecule
The for
or on
free-energy thethe
occurs
value
freeasthe
when
acceptor,
difference energy
reaction
shown
between of
in Figur
the
0 q* que elqAtuneleo qsea eficiente,
Para los niveles de energía de donador y aceptor deben
scales for these environmental fluctuations are typi
with value
ser muy parecidos: fluctuaciones the
asdelsimple
shown
than in
“solvente” two-state
theFigure
ayudan18.22.
tunneling
model
time. Just asofwethe
As a result, found
the
probabi
in the
net rate of
G p = probabilidad de estar
transition state,
channel canwe
ket ,(see find 7.1.2,
Section
be computed as p. 286), the probabili
T
q !G
las fluctuaciones (ns) son más rápidas que la transferencia (µs) en el estadoA de transición
q∗ = model
transition state in this two-state − 2 is .
k et 2 Tκq
=
−β("G−λ) kp , /4λ
A
18.22: Model free energies of pT ≈ e ∗
,
or–acceptor–solvent system We can use
where pT is the probability this
e −β!G
of findingresult to fin
the donor–
ituations when the electron is Wewecan usetransition
this result to pTthe
find = height ∗ . the ele
of ba
where have
the made the
stateadditional
characterized 1 assumption
+bye degenerate
−β!G th
onor molecule GD (q) and when middle state in Figure 18.21) and k is the tunneling∗ra
he acceptor molecule GA (q). much less than one, or, equivalently, that the!G free
With this result in hand,∗ we can∗ now(!G − λ)2 b
analyze
tion coordinate q representsIn light of this result, the !Gnet = Gelectron
D (q ) = transfer,
ear coordinates of the donor and driving-force
(A) dependence of the net 4λ electron
expression _
are inherited +from the _ where
quantity
2
λ =pκq. A /2 is the reo
acceptor as well as the solvent T + _ +
where 2 Physically,
is theintuition the reorganiza
of freedom. λ _= κqA /2
To develop
+
further +reorganization
about +the energy
probab in
_
2π 2 2
Physically, k _
between
+ the reorganization
fluctuation into the = |H +
ρe−β("G−λ)
the
energy
_ DA | state,
et transition acceptor
we nowstat
_ is the /4λ
co,
fr
! value
the for
between
sion of Marcus theory. The in
estado de transición the acceptor state idea is which
which to the the do
react
introduce
where thethe
H value
free for which theacceptor
_ +energy of to the
corresponds donor
_ ground
state
donor–acceptor–solvent
tunneling
state
is +at its (q
matrix min=s
el
κ es la amplitud DA
de las parábolas
_ +
duced acceptor
of
asaH inground
single Equation state (q
reaction+ 18.43,
+ = q
coordinate ). q, shown
Athough
_
here in Figu
with +
+
λ es la energía de reorganización +
+ _
Chaptercrete, thisAND
_ reaction coordinate captures the comp
746 realism 18demanded
LIGHT _by the
LIFE structure of the _ dono
degrees of freedom as they jiggle around. The
apter 18 LIGHT AND LIFE their environment. As mentioned earlier, the facto
and G(B)A (q) shown in the figure are an approxima
in detail in the appendix at the end of the chapter.
the free energy of the system when the electron
“chap18.tex” — thepage
surprising
746[#30]
ferred and counterintuitive
is either on the donor molecule predictionor onthath
fer rate thatcanis, actually
before ordecrease with increasing
after the electron transfer re d
page 746[#30]
ergy

ergy
shownThe by difference
the “inverted between region” that can be
the free-energy seena
minima
Se usan ~300 clorofilas para hacer un O2. 2480 clorofilas por O2
8-10 fotones por O2

el par especial absorbe fotones 10

veces por segundo, pero la reacción
hasta Q toma sólo 100 µs … hay que
pasarle excitones por resonancia en ps.

¿qué hacen las demás?

Son antenas.
 electric potential difference. To explore the free en
available by setting up the transmembrane ion grad
La energía de la luz se guarda en ATP y en NADPH.
N protons on one side of the membrane, resulting in

!!
G(N) = NqV − kB T ln .
N!(! − N)!

The first term accounts for the difference in electric

sured by the voltage V and the second term invokes
capture the conformational degrees of freedom of th
the trusted Stirling approximation (see p. 221), we
free energy as

G(N) = NqV − NkB T ln ! + kB TN ln N − NkB T

With this free energy in hand, we can now comput

romper agua: difference across the membrane as
~125 kT, cin
mucho más "G = q"V + kB T ln ,
cout
que un fotón
de luz visible; where we have used the same reasoning exploited
se usan 4 (p. 660). Given that the concentration of protons is
through c = 10−pH , we can rewrite the free-energy d

meta: generar un gradiente de protones "G = q"V − "pH kB T ln 10,

Romper agua requiere acumular la energía de cuatro fotones.
Con el ATP y el NADPH se reduce el CO2 a azúcar.
La fotosíntesis oxigénica “contaminó” la atmósfera con O2.
En los últimos 50 años ha aumentado la cantidad de CO2 en la
atmósfera, y ha disminuido la cantidad de O2.

sobre esta tendencia, hay una fluctuación anual à actividad de plantas

CO2 baja en verano, y sube en invierno

Fotosíntesis y respiración forman un ciclo de materia,
con el sol como combustible.
La fotosíntesis cubre 20 órdenes de magnitud en escala de tiempo.