Vibrational energy redistribution during donor–acceptor electronic energy transfer: criteria to identify subsets of active normal modes

Alfonso-Hernandez, Laura; Athanasopoulos, Stavros; Tretiak, Sergei; Miguel, Beatriz; Bastida, Adolfo; Fernández-Alberti, Sebastián

doi:10.1039/d0cp03102j

Cited by 15 publications

(23 citation statements)

References 85 publications

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“…Nevertheless, there is cumulative evidence that the vibrational energy redistribution in the direction of the nonadiabatic coupling vector may play a bigger role than usually expected. Fernandez-Alberti, Tretiak, and co-workers have shown for several classes of systems that the vibrational energy relaxation after a nonadiabatic transition is biased toward the nonadiabatic coupling vector’s direction. − Their analysis of vibrational energy redistribution revealed that only a small subset of normal modes with large overlap with the nonadiabatic coupling vector actively contributes to the electronic relaxation process. Sellner and co-workers have also shown that the exit direction from the conical intersection may be the main driver for forming specific photoproducts.…”

Section: Introductionmentioning

confidence: 99%

Velocity Adjustment in Surface Hopping: Ethylene as a Case Study of the Maximum Error Caused by Direction Choice

Barbatti

2021

J. Chem. Theory Comput.

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The most common surface hopping dynamics algorithms require velocity adjustment after hopping to ensure total-energy conservation. Based on the semiclassical analysis, this adjustment must be made parallel to the nonadiabatic coupling vector's direction. Nevertheless, this direction is not always known, and the common practice has been to adjust the velocity in either the linear momentum or velocity directions. This paper benchmarks surface hopping dynamics of photoexcited ethylene with velocity adjustment in several directions, including those of the nonadiabatic coupling vector, the momentum, and the energy gradient difference. It is shown that differences in time constants and structural evolution fall within the statistical uncertainty of the method considering up to 500 trajectories in each dynamics set, rendering the three approaches statistically equivalent. For larger ensembles beyond 1000 trajectories, significant differences between the results arise, limiting the validity of adjustment in alternative directions. Other possible adjustment directions (velocity, single-state gradients, angular momentum) are evaluated as well. Given the small size of ethylene, the results reported in this paper should be considered an upper limit for the error caused by the choice of the velocity-adjustment direction on surface hopping dynamics. LJ P L J(4)

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Section: Introductionmentioning

confidence: 99%

Velocity Adjustment in Surface Hopping: Ethylene as a Case Study of the Maximum Error Caused by Direction Choice

Barbatti

2021

J. Chem. Theory Comput.

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“…21 There have been reports of IVR that is slightly faster in a set of small amides in aqueous solution (4.9 ps for N-methylacetamide), 22 and a simulation study even propose IVR that is concomitant with the electronic transition. 23 The latter has not be experimentally verified so altogether 10 ps is a good ballpark number. The concept of IVR is a fairly theoretical approach to experimental femtochemistry, but herein it is assumed that it is a sensible vantage point for the description of molecular dynamics.…”

Section: ψ ⟩mentioning

confidence: 99%

“…The process of distributing the vibrational energy to the vibrational states that were not included in the formation of the original wave packet is referred to as intramolecular vibrational redistribution (IVR); the time scale involved is debatable and strongly dependent on the system (primarily rigidity and symmetry), but the consensus is that >10 ps is not too far off . There have been reports of IVR that is slightly faster in a set of small amides in aqueous solution (4.9 ps for N -methylacetamide), and a simulation study even propose IVR that is concomitant with the electronic transition . The latter has not be experimentally verified so altogether 10 ps is a good ballpark number.…”

Section: Introductionmentioning

confidence: 99%

Nonstatistical Photoinduced Processes in Gaseous Organic Molecules

Sølling

2021

ACS Omega

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Processes that proceed in femtoseconds are usually referred to as being ultrafast, and they are investigated in experiments that involve laser pulses with femtosecond duration in so-called pump probe schemes, where a light pulse triggers a molecular process and a second light pulse interrogates the temporal evolution of the molecular population. The focus of this review is on the reactivity patterns that arise when energy is not equally distributed on all the available degrees of freedom as a consequence of the very short time scale in play and on how the localization of internal energy in a specific mode can be thought of as directing a process toward (or away from) a certain outcome. The nonstatistical aspects are illustrated with examples from photophysics and photochemistry for a range of organic molecules. The processes are initiated by a variety of nuclear motions that are all governed by the energy gradients in the Franck–Condon region. Essentially, the molecules will start to adapt to the new electronic environment on the excited state to eventually reach the equilibrium structure. It is this structural change that is enabling an ultrafast electronic transition in cases where the nuclear motion leads to a transition point with significant coupling between to electronic states and to ultrafast reaction if there is a coupling to a reactive mode at the transition point between the involved states. With the knowledge of the relation between electronic excitation and equilibrium structure, it is possible to predict how the nuclei move after excitation and often whether an ultrafast (and inherently nonstatistical) electronic transition or even a bond breakage will take place. In addition to the understanding of how nonstatistical photoinduced processes proceed from a given excited state, it has been found that randomization of the energy does not even always take place when the molecule takes part in processes that are normally considered statistical, such as for example nonradiative transitions between excited states. This means that energy can be localized in a specific degree of freedom on a state other than the one that is initially prepared. This is a finding that could kickoff the ultimate dream in applied photochemistry; namely light excitation that leads to the rupture of a specific bond.

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“…One final comment is that the vibrational mode identities in such a complex system containing TbAcI and the quencher are generally not preserved during electronic dynamics because of normal mode mixing. [43]…”

Section: F I G U R Ementioning

confidence: 99%

A stable and sensitive luminescent photoprobe based on tris(3‐acetylindole) terbium(III) complex: Molecular modeling, luminescence quenching, and Ab initio molecular dynamics

Elsaady

Youssef

Attia

et al. 2020

Applied Organom Chemis

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We have been successfully used a new photoprobe based on Tb(III) (3-acetyleindole) 3 complex (TbAcI) as a novel, sensitive, accurate, and precise sensor for detecting shallow concentration (pico) of epinephrine (EPI) in different serum samples. Here, we report on and discuss the molecular structure of the interacting species using density functional theory (DFT) and timedependent density functional theory (TD-DFT). The simulation results reveal the strong binding energy of TbAcI (−148.95 kcal/mol) and explain the outcomes of Stern-Volmer bimolecular quenching analysis due to EPI's presence in the proximity (at 3.22 Å apart from Tb ion) of the emissive TbAcI. The bimolecular quenching rate constant (k 2) obtained from the Stern-Volmer rate constant (K sv) and the complex luminescence lifetime points to a diffusioncontrolled dynamic quenching. We used the Ab initio molecular dynamic (AIMD) simulations to explain EPI's effect on the TbAcI molecular kinetic energy changes in its S 1 state. Quenching begins at 14 fs when the EPI-TbAcI distance is about 3.22 Å. The excited state AIMD simulations proposes a new opportunity for future research on luminescence quenching.

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Vibrational energy redistribution during donor–acceptor electronic energy transfer: criteria to identify subsets of active normal modes

Abstract: Photoinduced electronic energy transfer in conjugated donor-acceptor systems is naturally accompanied by intramolecular vibrational energy redistributions accepting an excess of electronic energy. Herein, we simulate these processes in a covalently...

Cited by 15 publications

References 85 publications

Velocity Adjustment in Surface Hopping: Ethylene as a Case Study of the Maximum Error Caused by Direction Choice

Velocity Adjustment in Surface Hopping: Ethylene as a Case Study of the Maximum Error Caused by Direction Choice

Nonstatistical Photoinduced Processes in Gaseous Organic Molecules

A stable and sensitive luminescent photoprobe based on tris(3‐acetylindole) terbium(III) complex: Molecular modeling, luminescence quenching, and Ab initio molecular dynamics

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