Fundamental Approaches to Nonadiabaticity: Toward a Chemical Theory beyond the Born–Oppenheimer Paradigm

Yonehara, Takehiro; Hanasaki, Kota; Takatsuka, Kazuo

doi:10.1021/cr200096s

Cited by 194 publications

(229 citation statements)

References 259 publications

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“…The latter effect can be partially mitigated using socalled decoherence corrections; the interested reader is referred to the according literature. [132,[136][137][138][139][140][141][142][143][144][145][146][147][148][149][150][151][152][153] Tunneling effects can also not be described with surface hopping although there exist several approaches to alleviate this deficiency, see, for example, Refs. [154][155][156][157][158].…”

Section: Dynamics Simulations Of Intersystem Crossingmentioning

confidence: 99%

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Mai

Marquetand

González

2015

Int J of Quantum Chemistry

271

406

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Intersystem crossing is a radiationless process that can take place in a molecule irradiated by UV‐Vis light, thereby playing an important role in many environmental, biological and technological processes. This paper reviews different methods to describe intersystem crossing dynamics, paying attention to semiclassical trajectory theories, which are especially interesting because they can be applied to large systems with many degrees of freedom. In particular, a general trajectory surface hopping methodology recently developed by the authors, which is able to include nonadiabatic and spin‐orbit couplings in excited‐state dynamics simulations, is explained in detail. This method, termed SHARC, can in principle include any arbitrary coupling, what makes it generally applicable to photophysical and photochemical problems, also those including explicit laser fields. A step‐by‐step derivation of the main equations of motion employed in surface hopping based on the fewest‐switches method of Tully, adapted for the inclusion of spin‐orbit interactions, is provided. Special emphasis is put on describing the different possible choices of the electronic bases in which spin‐orbit can be included in surface hopping, highlighting the advantages and inconsistencies of the different approaches. © 2015 Wiley Periodicals, Inc.

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Section: Dynamics Simulations Of Intersystem Crossingmentioning

confidence: 99%

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Mai

Marquetand

González

2015

Int J of Quantum Chemistry

271

406

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“…A major drawback of Ehrenfest dynamics is that it fails to achieve thermal equilibrium, 39,40 e.g., non-Boltzmann distribution of equilibrium state population, and does not properly account for decoherence. [41][42][43] Several approaches are being debated in the literature to improve long-time behavior [44][45][46] and incorporate decoherence effects 41,47 in Ehrenfest dynamics, but they are outside the scope of our analysis.…”

Section: Reduced Density Matrix Dynamicsmentioning

confidence: 99%

Charge Dynamics in Organic Photovoltaic Materials: Interplay between Quantum Diffusion and Quantum Relaxation

2015

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Original citation:Lee, Myeong H., Aragó, Juan and Troisi, Alessandro. (2015) Charge dynamics in organic photovoltaic materials : interplay between quantum diffusion and quantum relaxation. The Journal of Physical Chemistry Part C, 119 (27). pp. 14989-14998. Permanent WRAP url:http://wrap.warwick.ac.uk/73402 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Part C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work, see http://dx.doi.org/10.1021/acs.jpcc.5b03989 A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. For more information, please contact the WRAP This paper discusses the mechanism of generation of free charges in organic photovoltaic cells (OPV) from electrostatically bound electron-hole pairs. The efficiency of this process is explained when interfacial charge-transfer (CT) states are generated by direct optical excitation. We used semiclassical quantum dynamics at short timescale (∼100 fs) and Redfield theory at relatively long timescale (∼10-100 ps) to cover both the process of dissociation and the relaxation to the lowest energy state. Our calculations suggest that a CT state with an intermediate electron-hole separation can evolve into a charge-separated (CS) state on ultrafast timescales (∼100 fs) as a result of quantum diffusion. On long timescales, however, the CS states ultimately relax to the low-energy CT states due to the interaction with the thermal bath, indicating that the yield of free charge carrier generation is determined by the interplay between ultrafast charge separation, due to quantum diffusion, and the much slower quantum relaxation process.

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“…The Ehrenfest method has been extensively discussed in the literature [16][17][18][19][20][21][22][23][24][25][26]. In this section, we review the Ehrenfest formalism following the elegant derivation of Tully [27].…”

Section: The Ehrenfest Approach: General Theoretical Developmentmentioning

confidence: 99%

The second-order Ehrenfest method

et al. 2014

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This article describes the Ehrenfest method and our second-order implementation (with approximate gradient and Hessian) within a CASSCF formalism. We demonstrate that the second order implementation with the predictor-corrector integration method improves the accuracy of the simulation significantly in terms of energy conservation. Although the method is general and can be used to study any coupled electron-nuclear dynamics, we apply it to investigate charge migration upon ionization of small organic molecules, focusing on benzene cation. Using this approach, we can study the evolution of a non-stationary electronic wavefunction for fixed atomic nuclei, and where the nuclei are allowed to move, to investigate the interplay between them for the first time. Analysis methods for the interpretation of the electronic and nuclear dynamics are suggested: we monitor the electronic dynamics by calculating the spin density of the system as a function of time.

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Fundamental Approaches to Nonadiabaticity: Toward a Chemical Theory beyond the Born–Oppenheimer Paradigm

Cited by 194 publications

References 259 publications

A general method to describe intersystem crossing dynamics in trajectory surface hopping

A general method to describe intersystem crossing dynamics in trajectory surface hopping

Charge Dynamics in Organic Photovoltaic Materials: Interplay between Quantum Diffusion and Quantum Relaxation

The second-order Ehrenfest method

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