Probing quantum coherence in ultrafast molecular processes: An <i>ab initio</i> approach to open quantum systems

Coccia, Emanuele; Troiani, Filippo; Corni, Stefano

doi:10.1063/1.5022976

Cited by 25 publications

(53 citation statements)

References 115 publications

(157 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As a consequence of the mixing, the lifetime of states with the photon partially absorbed is extended up to hundreds of fs, depending on the strong coupling conditions. Within our model, we adapt a quantum jump algorithm [68][69][70][71] already exploited in the Stochastic Schrödinger Equation (SSE) framework [72] to account for relaxation and dephasing channels. Stochastic methods in the framework of SSE are also commonly exploited as an equivalent alternative to master equations in treating cavity losses.…”

Section: Cavity Lossesmentioning

confidence: 99%

Photochemistry in the strong coupling regime: A trajectory surface hopping scheme

et al. 2020

Self Cite

View full text Add to dashboard Cite

The strong coupling regime between confined light and organic molecules turned out to be promising in modifying both the ground state and the excited states properties. Under this peculiar condition, the electronic states of the molecule are mixed with the quantum states of light. The dynamical processes occurring on such hybrid states undergo several modifications accordingly. Hence, the dynamical description of chemical reactivity in polaritonic systems needs to explicitly take into account the photon degrees of freedom and nonadiabatic events. With the aim of describing photochemical polaritonic processes, in the present work, we extend the direct trajectory surface hopping scheme to investigate photochemistry under strong coupling between light and matter.

show abstract

Section: Cavity Lossesmentioning

confidence: 99%

Photochemistry in the strong coupling regime: A trajectory surface hopping scheme

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…Diagonal and off-diagonal elements of the reduced density matrixρ S (t), respectively populations and coherences of the states of the system at time t, are obtained by averaging on the number of independent realizations N traj of SSE [41]. Given the definition of the reduced density matrixρ…”

Section: A Stochastic Schrödinger Equationmentioning

confidence: 99%

“…where C(t) is the vector of the time-dependent expansion coefficients and H SSE (t) is the matrix representation at time t ofĤ SSE (t) in the basis of the CIS eigenstates (H SSE (t)) kl = k|Ĥ SSE (t)|l . Coefficients C(t) are propagate via a second-order Euler algorithm [41].…”

Section: Cis Expansion Of the Wave Functionmentioning

confidence: 99%

See 1 more Smart Citation

Role of coherence in the plasmonic control of molecular absorption

Coccia

Corni

2019

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

The interpretation of nanoplasmonic effects on molecular properties, such as metal-enhanced absorption or fluorescence, typically assumes a fully coherent picture (in the quantum-mechanical sense) of the phenomena. Yet, there may be conditions where the coherent picture breaks down, and decoherence effect should be accounted for. Using a state-of-the-art multiscale model approach able to include environment-induced dephasing, here we show that metal nanoparticle effects on the light absorption by a nearby molecule is strongly affected (even qualitatively, i.e., suppression vs enhancement) by molecular electronic decoherence. The present work shows that decoherence can be thought as a further design element of molecular nanoplasmonic systems.

show abstract

“…48 In practice, the time-dependent approach amounts to numerically solve a time-dependent Schrödinger equation for the molecule (or its DFT counterpart, i.e., a time-dependent Kohn-Sham equation) electromagnetically coupled to a numerical time-dependent classical electromagnetic solver. 49,50 The Finite Difference Time Domain solver coupled to real-time TDDFT is the most natural choice. [51][52][53][54] A time-dependent formulation of the ASC approach is also possible and may have technical advantages in the calculation of the electromagnetic coupling.…”

mentioning

confidence: 99%

Multiscale modelling of photoinduced processes in composite systems

2019

Self Cite

View full text Add to dashboard Cite

| In the last decades, the quantum mechanical modeling has moved from isolated molecules made of few atoms, to large supramolecular aggregates embedded in complex environments. This has been made possible by the important progress achieved by multiscale models based on the integration of QM methods with classical descriptions. One of the first example of this integration is represented by continuum solvation models that starting from the eighties of the last century have been largely and successfully applied to predict properties and processes of solvated molecules. Almost in the same years, another alternative classical description, based on Molecular Mechanics (MM) has been coupled to QM methods to give the hybrid QM/MM approach. Since their first formulations, these QM/classical models have seen an enormous development in terms of accuracy, robustness and generalizability. This progress has allowed their application to systems of increasing complexity and to processes never faced before within a QM framework. An important example of such an achievement is represented by the novel insights reached in the fundamental understanding and the possible exploitation of photoinduced processes in biomolecules, nanomaterials and, more in general, composite systems where different "objects" of molecular, nano and mesoscopic scale are coupled together. In this review, we highlight the potentials and the limitations of such modeling, thereby showing which developments are still needed to definitely make the QM-based multiscale strategy the gold-standard for explaining the outputs of novel advanced spectroscopic techniques and predicting the outcome of light-activated events in composite systems. The multiscale strategiesIn the years, two main strategies to combine QM descriptions of the target and classical models of the environment, have been proposed. Interestingly, their first formulations date back to the same years, namely the end of the seventies of the previous century. [8][9][10] The two strategies refer to continuum and discrete (or atomistic) descriptions of the environment, respectively. In the latter case, the atoms of the environment (or group of atoms in coarser grained versions of the model) are treated through a Molecular Mechanics (MM) force field (FF). [11][12][13][14][15] In the former case, instead, the atomic nature of the environment is lost and a continuum description in terms of macroscopic properties is introduced instead. 16-18 Despite this huge "modellistic" difference, the two formulations present important common elements when reconsidered from the point of view of the QM target. In any case, for simplicity's sake two separate presentations will be given. QM/continuum. If the environment loses its atomic nature, an effective description has to be introduced which is based on some macroscopic properties. This is exactly what is done in continuum models where the target sees the environment as an infinite dielectric medium characterized by a (generally) frequency and position dependent permittivit...

show abstract

Probing quantum coherence in ultrafast molecular processes: An ab initio approach to open quantum systems

Cited by 25 publications

References 115 publications

Photochemistry in the strong coupling regime: A trajectory surface hopping scheme

Photochemistry in the strong coupling regime: A trajectory surface hopping scheme

Role of coherence in the plasmonic control of molecular absorption

Multiscale modelling of photoinduced processes in composite systems

Contact Info

Product

Resources

About