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# Femtochemistry

:
A theoretical overview
VI – Transition probabilities

Mario Barbatti
mario.barbatti@univie.ac.at
http://homepage.univie.ac.at/mario.barbatti/fem
tochem.html

Fermi’s golden rule

2

Fermi’s Golden Rule

Transition rate:

2
2
Wk 
i H p k k

k , k

Quantum levels of
the non-perturbed
system



Perturbation is
applied

i
Transition is
induced

3

Derivation of Fermi’s Golden Rule • See Fermi‘s Golden Rule paper at the course homepage Time-dependent formulation    i   H 0 t  H  H0  H p H0 – Non-perturbated Hamiltonian Hp – Perturbation Hamiltonian n  H 0  En  n  0 which solves: i j   ij and Ei  E j  ij 4 .

Derivation of Fermi’s Golden Rule    an  t  e iEnt n n H  H0  H p  i   H    0    t  Multiply by k at left and integrate Prove it! i ak  t    k H p n an  t  eiknt t n Note that the non-perturbated Hamiltonian is supposed non-depen 5 .

dak( p )  t  i   k H p n an( p 1)  t  e iknt dt n 6 .An approximate way to solve the differential equation i ak  t    k H p n an  t  e iknt t n Guess the “0-order” solution: an( 0 )  t  Use this guess to solve the equation and to get the 1st-order approximation: dak(1)  t  i   k H p n an( 0 )  t  e iknt dt n ak(1)  t  Use the 1st-order to get the 2nd-order approximation and so on.

First order approximation dak(1)  t  i   k H p n an( 0 )  t  eiknt dt n Guess the “0-order” solution: an( 0 )  t    ni Suppose the simplified perturbation:  H kn' k Hp n    0 Constant between 0 and  Otherwise k Hp n H kn' 0 t 0  7 .

First order approximation i kn t ' H  e  nm ni  da  t  i  dt  (1) k i a (1) k    H It was used: ' ik   0  a 0 e n i ki t Otherwise 0 ' i kn / 2 ik dt  2 H e e dx  2e ikx Between 0 and  ikx / 2 sin  ki / 2  ki sin  kx / 2 k 8 .

2 0.6 2 sin( ) / ' 2 ik 0.0 0  9 . 0. only transitions with  ~ 0 take place. 1.Transition probability Pik  ak    4 H 2 0.8 2 sin 2  ki / 2   2 ki2 In this derivation for constant perturbation. 0.4 The final result for the Fermi’s Golden Rule is still the same.  ≠ 0 can occur.0 If the perturbation oscillates harmonically (like a photon).

Physically meaningful quantity 1 Wk   Pik '  k ' near k k . k i Near k: density of states dn k  dE 1 1  Wk   Pik '   Pik  k dEk   Pik  k dki  k ' near k   10 .

Physically meaningful quantity Wk  Using 1 1  P  P  dE  Pik  k dki  ik ' ik k k    k ' near k   Pik  4 H ' 2 ik sin 2  ki / 2   2 ki2 1 1 sin 2  ki / 2  ' 2 Wk  4 H ik  k  dki 2    ki    /2 2 ' 2 Wk  H ik  k  11 .

k   i 12 .Fermi’s Golden Rule: photons and molecules H  H0  d  E Transition rate: H0 – Non-perturbated molecular Hamiltonian d  E – Light-matter perturbation Hamiltonian Wk  2  2 i d k   e iik t Edt  k  0 k .

Transition dipole moment Wk  2  2 i d k   e iik t Edt  k  0  0 i d k  i e N at   Z R  r n 1  N el n n m 1 m  k  d N  ik  i d e k  k . k  Electronic transition dipole moment  i 13 .

Einstein coefficients (see Einstein coefficients text in the course hom Wika  Bik N i Rate of absorption i → k Einstein coefficient B for absorption 1 gk Bik  i de k 2 6 0  g i 2 g n .degeneracy of state n k ik ik Ni i 14 .

Einstein coefficients Rate of stimulated emission k → i Wkist  Bki N k Einstein coefficient B for stimulated emission gi Bik  Bki gk Nk k ki ki i 15 .

Einstein coefficients Rate spontaneous decay k → i Wkisp  Aki N 2 Einstein coefficient A for spontaneous emission ki3 Aki  2 3 Bki  c Nk k ki ki i 16 .

Einstein coefficient and oscillator strength 2 0 mc 3 f ki   Aki 2 2 ki e In atomic units: c3 f ki   Aki 2 2Eki 17 .

4189 10 17 s   70 ns 18 .170884 au 3 (137)  21   2(0.65 eV and f21 = -0.015.29  1010 au Converting to nanoseconds:  21  0.211396  0.29 1010  2.65 eV  4. what is the lifetime of the excited state? R E21  4.170884) 2 (0.65 / 27.015)  0.Einstein coefficient and lifetime 3 1 c  ki   Aki 2E 2 f ki E 2 1 If E21 = 4.

what is the probability of ending in state 1 at x = ∞? E 2 . 2 1 . 1 x 0 20 . 1 2 . 2 H22 0 E2 H12 H11 E1 1 .Non-adiabatic transitions Problem: if the molecule prepared in state 2 at x = ∞ moves through a region of crossing.

Landau-Zener H11  H 22  F12 x H12 . Delos-Thorson. 5. Bradauk. Nikitin H11  H 22    A cos 0 exp   x  A H12   sin 0 exp   x  2 4. F12  constant  2 2 H12  P  exp    v F12  2. 6. …    E1  E2   P  sech  x  4  vh   12 2 exp  cos 2  0 / 2   1 P exp   1 2   tan 2 0 cot 2 0 v 21 .Models for non-adiabatic transitions 1. Demkov / Rosen-Zener E1  E2  constant h12  h12x sech x /   3.

Derivation of Landau-Zener formula i t     an  t  exp    H nn  t  dt  n    n   i    H  0 t  Multiply by k at left and integrate dak  t  i   H kn an  t  e n dt n k H kn  k H n i t  n    H nn dt  In the deduction it was used: d t H nn dt  H nn  dt 22 .

Since there are only two states: i dak  t    H kn an  t  e n dt nk da1  t  i   H12 a2  t  e 21 dt  (i) da2  t  i   H 21a1  t  e 12 dt  (ii)  ij   i   j Solving (i) for a2 and taking the derivative:  H11  H 22  e da1  ie d 2 a1  t   da2  t  (iii) 2 12 H12 12 dt H12 dt dt Substituting (iii) in (ii): d 2 a1 i da1 1 2   H11  H 22   2 H12 a1  0 2 dt  dt  23 .

d 2 a1 i da1 1 2   H  H   H 11 22 12 a1  0 2 2 dt  dt  Zener approximation: H11  H 22  t H11  F1 x  F1vt E 0 2 . 1 H 22  F2 x  F2 vt dH11  F1 dx 1 . 2 dH 22  F2 dx 1 . 1 H11  H 22   F1  F2 vt    F12 v x 0 24 . 2 2 .

 2  H12  a2      exp    v F12  a2      1 a1      ? a1      0 a2      ? (The complete derivation is in the paper on LandauZener in the course homepage) 0 x 0 25 .d 2 a1 i da1 1 2   F vt  H 12 12 a1  0 2 2 dt  dt  d 2 a2 i da2 1 2   F vt  H 12 12 a2  0 2 2 dt  dt  Problem: Find a2(+∞) subject to the initial condition a2(∞) The solution is: E = 1.

The probability of finding the system in state 2 is: Pnad  a2    2  2 2 H12   exp    v F12  The probability of finding the system in state 1 is: Pad  1  Pnad 1  2 2 H12   1  exp    v F12  1 Probability Pad Pnad Pnad Pad 0 0 0 2 |H12| 0 | F12| or v 26 .

75 -224.03224    0.80 cs H11 =  t -224.01126   0.65 cs  * H12 =  au -224.Example: In trajectory in the graph. what are the probability of the molecule to remain in the * state or to change to the closed shell state? P * *     F12 v H12   exp  2     2  1 H11  H 22  t   0.001 au 1 au time  2.85 0 2 4 6 8 Time (fs) 10 12 14 27 .70  * -224.0435 au/fs  0.4  10  2 fs  H22 =  t Energy (au) -224.

what are the probability of the molecule to remain in the * state or to change to the closed shell state? P * *  0.011577 2   exp  2   0.70  * -224.65 cs  * -224.001   P *cs  1  P * *  0.57 Energy (au) -224.80 cs -224.43 -224.75 0.57 0.85 0 2 4 6 8 Time (fs) 10 12 14 28 .Example: In trajectory in the graph.43 0.

Landau-Zener predicts: Adiabatic Non-adiabatic (diabatic) E E v v H12 0 0 x 0 Pnad  x 2 H12   exp    v F12  2 0 29 .For the same H12.

x For the same h12 . Rosen-Zener predicts: Adiabatic Non-adiabatic (but not diabatic!) E E v v 0 0 x 0 Pnad    E1  E2    sech  x  4  vh   12 x 0 2 30 .

For the same 0 (H12). Nikitin predicts: Adiabatic Non-adiabatic (diabatic) E E v 0 v  0 x 0 exp  cos 2  0 / 2    1 Pnad  exp   1 2   tan 2 0 cot 2 0 v x 0 31 .

If we want to perform dynamics. it is necessary to have the instantaneous probability. 32 .The problem with the previous formulations is that they only predict the total probability at the end of the process.

ppt 33 .ac.at This lecture can be downloaded at http://homepage.barbatti@univie.univie.ac.at/mario.ht ml lecture6.barbatti/femtochem.Next lecture Quantum dynamics methods Contact mario.