Surface hopping dynamics including intersystem crossing using the algebraic diagrammatic construction method

Mai, Sebastian; Plasser, Felix; Pabst, Mathias; Neese, Frank; Köhn, Andreas; González, Leticia

doi:10.1063/1.4999687

Cited by 34 publications

(70 citation statements)

References 105 publications

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“…Unlike their canonical counterparts, thiobases show exceptionally high‐ISC yields, usually in the range of 90–100%. With SHARC, the excited‐state dynamics of 2‐thiouracil (Mai, Marquetand, & González, ; Mai et al, ) and 2‐thiocytosine (Mai, Pollum, et al, ) was investigated. Figure , which is adapted from Mai, Marquetand, and González (), shows an example of the time evolution of the singlet and triplet states in 2‐thiouracil.…”

Section: Sharc Application Examplesmentioning

confidence: 99%

Nonadiabatic dynamics: The SHARC approach

Mai

Marquetand

González

2018

WIREs Comput Mol Sci

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We review the Surface Hopping including ARbitrary Couplings (SHARC) approach for excited‐state nonadiabatic dynamics simulations. As a generalization of the popular surface hopping method, SHARC allows simulating the full‐dimensional dynamics of molecules including any type of coupling terms beyond nonadiabatic couplings. Examples of these arbitrary couplings include spin–orbit couplings or dipole moment–laser field couplings, such that SHARC can describe ultrafast internal conversion, intersystem crossing, and radiative processes. The key step of the SHARC approach consists of a diagonalization of the Hamiltonian including these couplings, such that the nuclear dynamics is carried out on potential energy surfaces including the effects of the couplings—this is critical in any applications considering, for example, transition metal complexes or strong laser fields. We also give an overview over the new SHARC2.0 dynamics software package, released under the GNU General Public License, which implements the SHARC approach and several analysis tools. The review closes with a brief survey of applications where SHARC was employed to study the nonadiabatic dynamics of a wide range of molecular systems.This article is categorized under: Theoretical and Physical Chemistry > Reaction Dynamics and KineticsSoftware > Simulation MethodsSoftware > Quantum Chemistry

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Section: Sharc Application Examplesmentioning

confidence: 99%

Nonadiabatic dynamics: The SHARC approach

Mai

Marquetand

González

2018

WIREs Comput Mol Sci

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403

493

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“…and ADC(2): tUra 827,828 ), and kinetics (CASPT2: aza-tThy+O2 629 829 Computations studying these phenomena and the challenges present have been reviewed extensively in recent articles. 720,830 For multireference computations not only the general size of the system is demanding, but it is also particularly challenging to maintain a balanced distribution of the active orbitals over the involved nucleobases.…”

Section: Nucleobases and Derivativesmentioning

confidence: 99%

Multireference Approaches for Excited States of Molecules

et al. 2018

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Understanding the properties of electronically excited states is a challenging task that becomes increasingly important for numerous applications in chemistry, molecular physics, molecular biology, and materials science. A substantial impact is exerted by the fascinating progress in time-resolved spectroscopy, which leads to a strongly growing demand for theoretical methods to describe the characteristic features of excited states accurately. Whereas for electronic ground state problems of stable molecules the quantum chemical methodology is now so well developed that informed nonexperts can use it efficiently, the situation is entirely different concerning the investigation of excited states. This review is devoted to a specific class of approaches, usually denoted as multireference (MR) methods, the generality of which is needed for solving many spectroscopic or photodynamical problems. However, the understanding and proper application of these MR methods is often found to be difficult due to their complexity and their computational cost. The purpose of this review is to provide an overview of the most important facts about the different theoretical approaches available and to present by means of a collection of characteristic examples useful information, which can guide the reader in performing their own applications.

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“…The outcome of a chemical dynamics simulation in general depends strongly on an adequate sampling of initial conditions. 8 In practice, it is common to perform Wigner sampling in the harmonic approximation at zero temperature, 9,10 where one describes a molecule through a sum of uncoupled harmonic oscillators that are restricted to their vibrational ground state. Certainly, both approximations -the harmonic potentials and the zero-temperature formalism -are simplifications because realistic systems are anharmonic and possess a finite temperature.…”

Section: Introductionmentioning

confidence: 99%

Finite-temperature Wigner phase-space sampling and temperature effects on the excited-state dynamics of 2-nitronaphthalene

Zobel

Nogueira

González

2019

Phys. Chem. Chem. Phys.

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The concept of finite temperature Wigner phase-space sampling allowing the population of vibrationally excited states is introduced and employed to study temperature effects on the absorption spectrum of 2-nitronaphtalene (2NN) and its relaxation dynamics. It is found that, despite the fact that the general deactivation mechanism of 2NN after light irradiation does not change with increasing temperature, i.e., after excitation to the singlet manifold, 2NN deactivates via internal conversion in less than 100 fs and then undergoes intersystem crossing to the triplet manifold before decaying to the lowest triplet state in less than 150 fs, the intersystem crossing rate increases at higher temperatures. This increase is attributed to the appearance of a new deactivation pathway, which is not operative at lower temperatures. The present example illustrates that appropriate initial conditions beyond the idealized temperature of 0 K are indispensable to obtain reliable excited state mechanisms, which can be then related to experimental conditions.

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Surface hopping dynamics including intersystem crossing using the algebraic diagrammatic construction method

Cited by 34 publications

References 105 publications

Nonadiabatic dynamics: The SHARC approach

Nonadiabatic dynamics: The SHARC approach

Multireference Approaches for Excited States of Molecules

Finite-temperature Wigner phase-space sampling and temperature effects on the excited-state dynamics of 2-nitronaphthalene

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