Tracking an electronic wave packet in the vicinity of a conical intersection

Qi, Dalong; Duan, Hong-Guang; Sun, Zhenrong; Miller, R. J. Dwayne; Thorwart, Michael

doi:10.1063/1.4989462

Cited by 20 publications

(20 citation statements)

References 41 publications

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“…To obtain the stable Hamiltonian matrix, 20 ( Q t ) and 10 ( Q c ) vibrational levels are used in the tuning and coupling modes, respectively. To monitor the wave-packet dynamics on two reaction coordinates, we perform the projection calculation based on the theoretical work in ( 57 , 58 ).…”

Section: Methodsmentioning

confidence: 99%

Intermolecular vibrations mediate ultrafast singlet fission

Duan

Jha

et al. 2020

Sci. Adv.

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Singlet fission is a spin-allowed exciton multiplication process in organic semiconductors that converts one spin-singlet exciton to two triplet excitons. It offers the potential to enhance solar energy conversion by circumventing the Shockley-Queisser limit on efficiency. We study the primary steps of singlet fission in a pentacene film by using a combination of TG and 2D electronic spectroscopy complemented by quantum chemical and nonadiabatic dynamics calculations. We show that the coherent vibrational dynamics induces the ultrafast transition from the singlet excited electronic state to the triplet-pair state via a degeneracy of potential energy surfaces, i.e., a multidimensional conical intersection. Significant vibronic coupling of the electronic wave packet to a few key intermolecular rocking modes in the low-frequency region connect the excited singlet and triplet-pair states. Along with high-frequency local vibrations acting as tuning modes, they open a new channel for the ultrafast exciton transfer through the resulting conical intersection.

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Section: Methodsmentioning

confidence: 99%

Intermolecular vibrations mediate ultrafast singlet fission

Duan

Jha

et al. 2020

Sci. Adv.

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“…The particular CI case has been frequently dealt for instance with a perturbative Markovian Redfield approach 69 , time nonlocal second-order master equation 70 , Wigner distribution 45 , hybrid quantum master equation 71 , and recently beyond perturbative regime by HEOM 72,73 . One of the advantages is the accurate monitoring of the dissipative wave packet in the branching space that can be mapped by time and frequency resolved fluorescence spectroscopy 73 .…”

Section: Introductionmentioning

confidence: 99%

Statistical distributions of the tuning and coupling collective modes at a conical intersection using the hierarchical equations of motion

Mangaud

Lasorne

Atabek

et al. 2019

The Journal of Chemical Physics

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We investigate the possibility of extracting the probability distribution of the effective environmental tuning and coupling modes during the nonadiabatic relaxation through a conical intersection. Dynamics are dealt with an open quantum system master equation by partitioning a multistate electronic subsystem out of all the nuclear vibrators. This is an alternative to the more usual partition retaining the tuning and coupling modes of a conical intersection in the active subsystem coupled to a residual bath. The minimal partition of the electronic system generally leads to highly structured spectral densities for both vibrational baths and requires a strongly nonperturbative non-Markovian master equation, treated here by the hierarchical equations of motion (HEOMs). We extend—for a two-bath situation—the procedure proposed by Shi et al. [J. Chem. Phys. 140, 134106 (2014)], whereby the information contained in the auxiliary HEOM matrices is exploited in order to derive the nuclear dissipative wave packet, i.e., the statistical distribution of the displacement of the two tuning and coupling collective coordinates in each electronic state and the coherence. This allows us to visualize the distribution, all along the nonadiabatic decay. We explore a large parameter space for a symmetrical conical intersection model and a symmetrical initial Franck-Condon preparation. Some parameters could be controlled by external fields, while others are molecule dependent and could be designed by molecular engineering. We illustrate the relation between the strongly coupled electronic and bath dynamics together with a geometric measure of non-Markovianity.

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“…[13][14][15][20][21][22][23][24][25] In particular, recent theoretical studies on the isomerization dynamics in rhodopsin have emphasized that the degree of intramolecular vibrational coherence plays a crucial role for the quantum yield of photoproduct formation. 26,27 Despite multiple indications that the relative phase of vibrational modes may be important in rhodopsin photochemistry, 13,25,28 there is no direct experimental evidence suggesting its relevance for the chemical outcome, in particular with biologically relevant, incoherent excitation.…”

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confidence: 99%

Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision

et al. 2018

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Vibronic coupling is key to efficient energy flow in molecular systems and a critical component of most mechanisms invoking quantum effects in biological processes. Despite increasing evidence for coherent coupling of electronic states being mediated by vibrational motion, it is not clear how and to what degree properties associated with vibrational coherence such as phase and coupling of atomic motion can impact the efficiency of light-induced processes under natural, incoherent illumination. Here, we show that deuteration of the H-C=C-H double-bond of the 11-cis retinal chromophore in the visual pigment rhodopsin significantly and unexpectedly alters the photoisomerization yield while inducing smaller changes in the ultrafast isomerization dynamics assignable to known isotope effects. Combination of these results with non-adiabatic molecular dynamics simulations reveals a vibrational phase-dependent isotope effect that we suggest is an intrinsic attribute of vibronically coherent photochemical processes.

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Tracking an electronic wave packet in the vicinity of a conical intersection

Cited by 20 publications

References 41 publications

Intermolecular vibrations mediate ultrafast singlet fission

Intermolecular vibrations mediate ultrafast singlet fission

Statistical distributions of the tuning and coupling collective modes at a conical intersection using the hierarchical equations of motion

Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision

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