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• Chinese Optics Letters
• Vol. 20, Issue 10, 100007 (2022)
Samrit Mainali, Fabien Gatti*, and Osman Atabek
Author Affiliations
• , CNRS, Université Paris-Saclay, 91405 Orsay, France
• show less
Samrit Mainali, Fabien Gatti, Osman Atabek. Laser control strategies in full-dimensional funneling dynamics: the case of pyrazine [Invited][J]. Chinese Optics Letters, 2022, 20(10): 100007 Copy Citation Text show less

Abstract

Motivated by the major role funneling dynamics plays in light-harvesting processes, we built some laser control strategies inspired from basic mechanisms such as interference and kicks, and applied them to the case of pyrazine. We are studying the internal conversion between the two excited states, the highest and directly reachable from the initial ground state being considered as a donor and the lowest as an acceptor. The ultimate control objective is the maximum population deposit in the otherwise dark acceptor from a two-step process: radiative excitation of the donor, followed by a conical-intersection-mediated funneling towards the acceptor. The overall idea is to first obtain the control field parameters (individual pulses leading frequency and intensity, duration, and inter-pulse time delay) for tractable reduced dimensional models basically describing the conical intersection branching space. Once these parameters are optimized, they are fixed and used in full-dimensional dynamics describing the electronic population transfer. In the case of pyrazine, the reduced model is four-dimensional, whereas the full dynamics involves 24 vibrational modes. Within experimentally achievable electromagnetic field requirements, we obtain a robust control with about 60% of the ground state population deposited in the acceptor state, while about 16% remains in the donor. Moreover, we anticipate a possible transposition to the control of even larger molecular systems, for which only a small number of normal modes are active, among all the others acting as spectators in the dynamics.
 $HS(Q)=∑n|n〉Hnn(Q)〈n|+∑n≠m|n〉Hnm(Q)〈m|,$(1)

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 $Hnn(Q)=ϵ˜(n)+∑αNα[Pα2+ωα(n)2(Qα−dα(n))2],$(2)

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 $Hnm(Q)=∑αNαλα(nm)Qα,$(3)

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 $Hnn(Q)=ϵ(n)+∑αNα(Pα2+ωα(n)2Qα2)+∑αNακα(n)Qα,$(4)

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 $|ΨTot(Q,t)〉=∑n=13Ψn(Q,t)|n〉.$(5)

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 $−iℏ∂∂tΨn(Q,t)=HnnΨn(Q,t)+∑m≠nHnmΨm(Q,t).$(6)

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 $Ψn(Q,t)=∑JNJAJ,n(t)ΦJ,n(Q).$(7)

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 $Ψn(Q,t)=∑j1=1n1…∑jf=1nfAj1,…jf(t)∏α=1fφjα(α)(Qα,t),$(8)

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 $φjα(α)(Qα,t)=∑iαMαciα(α,jα)(t)χiα(α)(Qα).$(9)

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 $Q˜κ≡(Qκ,1,Qκ,2,…,Qκ,d),$(10)

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 $φj(κ)(Q˜κ,t)=φj(κ)(Qκ,1,Qκ,2,…,Qκ,d,t),$(11)

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 $Ψ(Q˜1,…,Q˜p,t)=∑j1⋯jpn1⋯npAj1⋯jp(t)∏κ=1pφj(κ)(Q˜κ,t),$(12)

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 $φj(κ)(Q˜κ,t)=∑i1⋯idMκ1⋯MκdCi1⋯id(κ,j)(t)χ(κ,1)(Qκ,1)⋯χ(κ,d)(Qκ,d).$(13)

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 $Pn(t)=∫|Ψn(Q,t)|2dQ.$(14)

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 $H(Q;t)=HS(Q)+V(Q;t),$(15)

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 $V(Q;t)=−μ(Q)E(t).$(16)

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 $μ01(Q)=ξ10a(01)Q10a,$(17)

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 $μ02(Q)=μ02(0)+∑α≠10aξα(02)Qα+12ρ10a(02)Q10a2.$(18)

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 $p˜(t)=P1(t)−P2(t)P0(t).$(19)

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 $p˜(t)=r(t)−11/P2(t)−[r(t)+1].$(20)

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 $p=1tmax−tmin∫tmintmaxp˜(t)dt.$(21)

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 $E(t)=∑i=1NIEi(t)sin(ωt),$(22)

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 $Ei(t)=sin2[πT(t−ti)]H(t−ti)H(ti+T−τ),$(23)

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 $A=∫0∞E2(t)dt.$(24)

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 $A=a∫0∞ϵ2(t)dt.$(25)

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 $T1=V+VG0V,$(26)

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 $T1=〈S1|W121ES0−ES2+ℏωμ20E1|S0〉,$(27)

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 $T2=〈S1|μ01E2|S0〉,$(28)

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 $P1=|T1+T2e−iEτ/ℏ|2,$(29)

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 $P1=|T1+T1e−iEτ/ℏ|2.$(30)

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Samrit Mainali, Fabien Gatti, Osman Atabek. Laser control strategies in full-dimensional funneling dynamics: the case of pyrazine [Invited][J]. Chinese Optics Letters, 2022, 20(10): 100007