Derivation of the LandauZener Formula

Outline
-Introduction-landau-zener formula
-Wittig introduces a simpler method of deriving the landauzener formula
-

choosing a state psi in the diabatic basis

putting in the time dependent S. eq. and deriving the equations of motion for
A&B first&second derivatives
under the assumption tha E12 =at we get the famous eq.6
finding the perturbative limit which is th LZ formula for non-adiabatic
transition- this allows for B=1 and to neglect d2B/dt2
now we wish to find the exact solution and see if in the perturbative limit
it matches the LZ-formula
we take eq.6 and integrate it and solve integral 2.1& 2.2
reaching a similar solution as in the perturbative case
QED

The LandauZener formula: exact solution to a one-dimensional semi-classsical

model for nonadiabatic transitions dynamics of a 2-level quantum mechanical

system,
a time-dependent Hamiltonian
nuclear motion is treated classically, in which case, it enters the electronic transition
problem as an externally controlled parameter

The formula was published separately by Lev Landau and Clarence Zener in 1932.
a set of simplifications are made, known collectively as the LandauZener
approximation:
1. The perturbation parameter in the Hamiltonian is a known, linear function of
time E12=t
2. the slopes of the intersecting potentials F1,F2are constant (and have the same,
negative, sign)
3. H12, the coupling matrix element in the diabatic basis, is constant
(The assumption that F1, F2, and H12 are each constant takes into account the fact that,
for a diabatic basis, these parameters change over distances (say a0) that are large
compared to the interaction region near the crossing point)
Nuclear motion enters parametrically.

In this talk I will present a more transparent solution is provided by Wittig

using contour integration.

A short explanation on complex analysis

In the diabatic 1,2 basis, the wave function is given by

A1 exp i E1dt B2 exp i E2 dt (1)

Choosing the initial state as 2
B0=1
Putting into the time-dependent Schrdinger equation

where E12 = E1 E2.

Further differentiation

Assumption:

[4]

E12 t
F12 F1 F2 0 0

vF12 Const

What is the value of B(t )?

We want B& 0 as t
obvious on physical grounds, because interaction ceases at t =
Thus, any phase oscillation that B might have must become immaterial at
sufficiently long times hard to see from the equations
Under the assumption E12 = t, where is a constant
E12 = t, eq 5 becomes
&
& i tB& H 2 B 0 (6)
B
12
the equation to be solved.
The desired quantity is the value of B after all interaction has ceased

The perturbative limit

Complex integral 1:

|H12| 0

=> B (t )

B 1
2
x
a
2
dx
a

1
2

t
1
2

dt

2
Af iH12
a

dx exp ix
2

dz dx

exp iz 2 exp ix 2

dz idy

exp iz 2 exp i x0 iy

exp i x

y 2 2 x0 y

z 1 i x

dz 1 i dx

exp iz 2 exp 2 x 2
x0

x0

dx exp ix dy exp i x
2

i
exp
2
4

2
Af H12
a

1
2

i
exp

Pna 1 A f 2 1 12 d B f 2

y 2 x0 y 1 i dx exp 2 x 2

Re 0
x

lim x

x0

12 |H12|/ - a characteristic frequency. For example, at x = 0 (see Figure 1), it is the

Rabi frequency with which the system oscillates between diabats
d |H12|/v|F12- the duration of the interaction, which we take to be l/v,
l is an interaction length given by |H12|/|F12|.

See that in the limit in which the system evolves mainly on a single diabat.
The probability that a nonadiabatic transition has taken place is slightly less than
unity.
The exact solution of eq 6, when taken to this limit(|H12| 0
must yield eq 9

=> B (t )

Derivation of the t Solution

1),

eq 6 yields Bf in just a few steps that involve contour integrations, obviating the need
to solve the second-order differential equation directly (simpler approach than zener's)

&
& i tB& H 2 B 0 (6)
B
12
Dividing eq 6 by B and Multiplying eq 6 by dt/t and integrating from to +

Complex integral 2

Functions are not defined at t=0

Bf

&
& t
dB
dt
dt B
i
H12
B
t t B t
1

Cauchy principal value:

When a pole lies on the contour of integration

f x dx

2 i Re z f z

f x dx

2 i
R

enclosed
poles

Re z f z i

Integral 2.1 (first left-hand term):

poles
on
contour

Re z f z

The function has a simple pole at z=0

z
Re z f z lim z z0 f z lim 1
z
z z0

z z0

id i

dz
dt

z t id i Re z f z i
R

dt
0
t

Integral 2.2 (second left-hand term):

Why is B/B analytical??

&
&and eq. 6 becomes
as t approaches infinity we neglect B
Integrating( separation of variables)
The time dependence of B is due to phase variation
Differentiation of eq 11 shows that:
&
&/B approaches zero as t-2, in accord with our neglect of
1) for t . - B
&
&
B
&
&(0)/B(0) is equal to |H12|2.
2) in the limit t 0, eq 6 indicates that B
This appears later as an integration residue.

The function behaves as 1/tn (poles only on the real axis)

&
&dz B
&
&dt B
&
&
B

B z B t B id
&
&
B
2
lim H12
t 0 B
&
&
B
lim 0
t B
2 z
2
Re z f z lim z z0 f z lim H12
H12
z
z z0
z z0
&
&dz B
&
&dt B
&
&
B
2

B z B t B id i Re z f z H12 i

R
0

&
&dt
B
2
i H12 2 i
t

H12 2

B f exp
2 exp 212 d __ 15

where = v|F12| has been used, with 12 = |H12| and d = |H12|/v|F12|.

Checking the perturbative limit:

In the limit |H12| 0, eq 15 must yield the expression for |Bf|2 given by eq 9
(expanding the exponent as a taylor series ,possible for a small H), which was derived
for this perturbative limit
this is in accord with the perturbative limit, Pna is given by

The general case of nonconstant slopes F1 and F2 and velocity v

eq 12 is written
is no longer constant

problems with the LZS formalism

there have
been many important aspects of the LZS curve crossing probelms left
unsolved:
-the LZS theory does not work with energies lower than the crossing point
-there is no good formula describing transmittion when the two potentials
have opposite slope signs
- the need for complex integration

-LZS formula requires knowledge of the diabatic potentials

-accurate phases to define the scattering matrix are not available for all
cases

nakamura

complete solutions for:

1.Landau-Zener (LZ) type- in which the two diabatic potential curves cross
with the same sign of slopes
2.Nonadiabatic tunneling (NT) type- in which the
potentials cross with different signs of slopes.

nice features :
(1) All the probabilities are expressed in simple analytical forms.
(2) All the necessary phases are provided in compact analytical forms.
(3) All the basic parameters can be directly estimated only from adiabatic potentials
on the real axis. This means that
(1) no-unique diabatization is needed
(2) no complex calculus is necessary, and
(3)no nonadiabtic coupling information is required
Furthermore, the theory works for whole range of energy and coupling strength for
general curved potentials.

Addendum

Diabatic/adiabatic: In quantum chemistry, the potential energy surfaces are obtained

within the adiabatic or Born-Oppenheimer approximation. This corresponds to a

representation of the molecular wave function where the variables corresponding to
the molecular geometry and the electronic degrees of freedom are separated. The non
separable terms are due to the nuclear kinetic energy terms in the molecular
Hamiltonian and are said to couple the potential energy surfaces. In the
neighbourhood of an avoided crossing or conical intersection, these terms cannot be
neglected. One therefore usually performs one unitary transformation from the
adiabatic representation to the so-called diabatic representation in which the nuclear
kinetic energy operator is diagonal. In this representation, the coupling is due to the
electronic energy and is a scalar quantity which is much more easy to estimate
numerically. low order Taylor series expansions of the surface capture much of the
complexity of the original system.
or the sake of argument, that only two Potential Energy Surfaces (PES), 1 and 2,
approach each other. Thus, we assume
making the expansion