The Born–Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered Describing dynamics when the Born–Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging Furthermore, it is necessary in order to connect with many ultrafast pump–probe spectroscopic experiments In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei Such ab initio quantum molecular dynamics methods solve the electronic Schrodinger equation alongsi

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Ab Initio Nonadiabatic Quantum Molecular Dynamics.

Nonadiabatic mixed quantum–classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods—mean-field Ehrenfest, trajectory surface hopping, and multiple spawning—this review focuses on the NA-MQC dynamics...

https://hal-amu.archives-ouvertes.fr/hal-01965458/document

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum-Classical Dynamics.

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.

Nonadiabatic dynamics: The SHARC approach

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.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/qua.24891

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

Electronically excited states of molecules are at the heart of photochemistry, photophysics, as well as photobiology and also play a role in material science. Their theoretical description requires highly accurate quantum chemical calculations, which are computationally expensive. In this review, we focus on not only how machine learning is employed to speed up such excited-state simulations but also how this branch of artificial intelligence can be used to advance this exciting research field in all its aspects. Discussed applications of machine learning for excited states include excited-state dynamics simulations, static calculations of absorption spectra, as well as many others. In order to put these studies into context, we discuss the promises and pitfalls of the involved machine learning techniques. Since the latter are mostly based on quantum chemistry calculations, we also provide a short introduction into excited-state electronic structure methods and approaches for nonadiabatic dynamics simulations and describe tricks and problems when using them in machine learning for excited states of molecules.

Machine Learning for Electronically Excited States of Molecules.

The dynamics of molecules under strong laser pulses is characterized by large Stark effects that modify and reshape the electronic potentials, known as laser-induced potentials (LIPs). If the time scale of the interaction is slow enough that the nuclear positions can adapt to these externally driven changes, the dynamics proceeds by adiabatic following, where the nuclei gain very little kinetic energy during the process. In this regime we show that the molecular dynamics can be simulated quite accurately by a semiclassical surface-hopping scheme formulated in the adiabatic representation. The nuclear motion is then influenced by the gradients of the laser-modified potentials, and nonadiabatic couplings are seen as transitions between the LIPs. As an example, we simulate the process of adiabatic passage by light induced potentials in Na2 using the surface-hopping technique both in the diabatic representation based on molecular potentials and in the adiabatic representation based on LIPs, showing how the ch...

Mixed quantum-classical dynamics in the adiabatic representation to simulate molecules driven by strong laser pulses.

We implemented a method for the treatment of field induced transitions in trajectory surface hopping simulations, in the framework of the local diabatization scheme, especially suited for on-the-fly dynamics. The method is applied to a simple one-dimensional model with an avoided crossing and compared with quantum wavepacket dynamics. The results show the importance of introducing a proper decoherence correction to surface hopping, in order to obtain meaningful results. Also the energy conservation policy of standard surface hopping must be revised: in fact, the quantum wavepacket energetics is well reproduced if energy absorption/emission is allowed for in the hops determined by radiation-molecule coupling. To our knowledge, this is the first time the issues of decoherence and energy conservation have been analyzed in depth to devise a mixed quantum-classical method for dynamics with molecule-field interactions.

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Interplay of radiative and nonradiative transitions in surface hopping with radiation-molecule interactions.

A comparative study of the ultrafast photodissociation dynamics of the dihalomethanes CH2ICl and CH2BrI has been carried out at 268 nm, around the maximum of the first absorption band, employing femtosecond velocity map ion imaging in conjunction with high level ab initio electronic structure calculations and full dimension on-the-fly trajectory calculations including surface hopping. Total translational energy distributions and angular distributions of the iodine fragments as well as reaction times for the C-I bond cleavage are presented and discussed along with the computed absorption spectra, potential energy curves and trajectories. The revealed dynamics is mainly governed by absorption to the 5A' state for CH2BrI while two dissociation pathways, through the 4A' or 5A' states, are in competition for CH2lCI. An anchor effect due to the substituent halogen atom (Br or Cl), which implies significant rotational motion of the dissociating molecule, characterizes the photodissociation in both dihalomethanes and leads to a remarkable rotational energy of the radical co-fragment. This energy flux into the internal degrees of freedom of the molecules is the main key factor governing the real time reaction dynamics.

Juan José Bajo

Papers

Mixed quantum-classical dynamics in the adiabatic representation to simulate molecules driven by strong laser pulses.

Interplay of radiative and nonradiative transitions in surface hopping with radiation-molecule interactions.

Halogen-atom effect on the ultrafast photodissociation dynamics of the dihalomethanes CH2ICl and CH2BrI.