In This Molecule There Must Be a Conical Intersection

Robb, Michael A.

doi:10.1016/b978-0-12-800256-8.00003-5

Cited by 20 publications

(15 citation statements)

References 99 publications

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“…(2) contains weak stimulated emission features relative to the dominant ESA and bleach peaks with vibronic progressions. Even at high excitation frequencies, where the ESA feature is weaker than the bleach signal, stimulated emission from the 1 MLCT bands appears weak, which is consistent with prior reports of ultrafast nonradiative decay to a 3 MLCT manifold through intersystem crossing [16]. The changes in the N719 spectra over time are significantly slower and subtler than the changes in the [IrBr6] 2spectra, with the most prominent change the shift in ESA excitation frequency from 500 THz at 3 ps to the excitation maximum of N719 (553 THz) at 800 ps.…”

Section: Resultssupporting

confidence: 90%

“…Measurments on rhodopsin, for instance, revealed that conical intersections can lead to internal conversion rates that are on the same timescales as vibrational relaxation [2]. Subsequent computational work suggested that conical intersections can act as mediators during photochemical reactions and exist as important bottlenecks in far more systems than previously thought possible [3].…”

Section: Introductionmentioning

confidence: 99%

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Characterizing divergent spin-orbit coupling effects on ultrafast nonradiative decay in transition-metal compounds

William

Daniel

2019

EPJ Web Conf.

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Section: Resultssupporting

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Characterizing divergent spin-orbit coupling effects on ultrafast nonradiative decay in transition-metal compounds

William

Daniel

2019

EPJ Web Conf.

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“…Conical intersections (CoIns) can be found in nearly every polyatomic molecule and dominate the outcome of many photochemical reactions (40). CoIns provide fast, sub-100-fs nonradiative decay channels that are defined by a strong coupling between nuclear and electronic degrees of freedom.…”

Section: Time-resolved Diffraction Movies Of Nonadiabatic Dynamicsmentioning

confidence: 99%

Monitoring molecular nonadiabatic dynamics with femtosecond X-ray diffraction

Bennett

Kowalewski

Rouxel

et al. 2018

Proc. Natl. Acad. Sci. U.S.A.

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Ultrafast time-resolved X-ray scattering, made possible by free-electron laser sources, provides a wealth of information about electronic and nuclear dynamical processes in molecules. The technique provides stroboscopic snapshots of the time-dependent electronic charge density traditionally used in structure determination and reflects the interplay of elastic and inelastic processes, nonadiabatic dynamics, and electronic populations and coherences. The various contributions to ultrafast off-resonant diffraction from populations and coherences of molecules in crystals, in the gas phase, or from single molecules are surveyed for core-resonant and off-resonant diffraction. Single-molecule [Formula: see text] scaling and two-molecule [Formula: see text] scaling contributions, where N is the number of active molecules, are compared. Simulations are presented for the excited-state nonadiabatic dynamics of the electron harpooning at the avoided crossing in NaF. We show how a class of multiple diffraction signals from a single molecule can reveal charge-density fluctuations through multidimensional correlation functions of the charge density.

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“…This "funnel" is likely to induce ultrafast decay since the non-adiabatic coupling becomes infinite at the CI. The latter is thus at the core of photochemical processes in excited states and is giving rise to a wide research area, both in advanced time-dependent spectroscopy [12][13][14][15] and in numerical simulations [16][17][18][19][20][21][22][23] . Alternatively, diabatic representations of the electronic states proa) Electronic mail: etienne.mangaud@sorbonne-universite.fr b) Electronic mail: benjamin.lasorne@umontpellier.fr c) Electronic mail: osman.atabek@u-psud.fr d) Electronic mail: michele.desouter-lecomte@u-psud.fr vide a smoother picture of the CI in the branching space 24,25 .…”

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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In This Molecule There Must Be a Conical Intersection

Cited by 20 publications

References 99 publications

Characterizing divergent spin-orbit coupling effects on ultrafast nonradiative decay in transition-metal compounds

Characterizing divergent spin-orbit coupling effects on ultrafast nonradiative decay in transition-metal compounds

Monitoring molecular nonadiabatic dynamics with femtosecond X-ray diffraction

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

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