SHARC: ab Initio Molecular Dynamics with Surface Hopping in the Adiabatic Representation Including Arbitrary Couplings

Abstract

We present a semiclassical surface-hopping method which is able to treat arbitrary couplings in molecular systems including all degrees of freedom. A reformulation of the standard surface-hopping scheme in terms of a unitary transformation matrix allows for the description of interactions like spin-orbit coupling or transitions induced by laser fields. The accuracy of our method is demonstrated in two systems. The first one, consisting of two model electronic states, validates the semiclassical approach in the presence of an electric field. In the second one, the dynamics in the IBr molecule in the presence of spin-orbit coupling after laser excitation is investigated. Due to an avoided crossing that originates from spin-orbit coupling, IBr dissociates into two channels: I + Br((2)P3/2) and I + Br*((2)P1/2). In both systems, the obtained results are in very good agreement with those calculated from exact quantum dynamical simulations.

Excited state dynamics of thiophene and bithiophene: new insights into theoretically challenging systems

“…78 On the other hand, weak phosphorescence was experimentally detected 79 (though not in another study 18 ) and that question is certainly awaiting additional theoretical investigation. The development of surface hopping with states of different multiplicities is still at its infancy, 80 but alternative schemes such as SHARC (surface hopping with arbitrary couplings) of González et al 81 and generalized trajectory surface hopping of Cui and Thiel 82 exist. One discouraging feature is that multireference methods might be overly expensive (and even challenging 39 ) for bithiophene, and even more for larger oligomers.…”

Femtosecond Intersystem Crossing in the DNA Nucleobase Cytosine

“…Such simulations are done using the newly developed surfacehopping method SHARC. 37 SHARC stands for surface hopping including arbitrary couplings. With SHARC, one can treat nonadiabatic and spin−orbit couplings (which mediate IC and ISC, respectively) on equal footing.…”

Derivation of spin-orbit couplings in collinear linear-response TDDFT: A rigorous formulation

“…This can be applied to study a wide range of interesting phenomena, such as molecular magnetism, spin transport, and spin quantum dots dynamics for quantum computing. Regarding our particular interests, we now have the capability to extend nonadiabatic on-the-fly trajectory based approaches such as Tully's trajectory surface hopping (TSH) [53][54][55] and nonadiabatic Bohmian Dynamics [56][57][58] to the dynamical study of intersystem crossing within LR-TDDFT, which are key to understanding many important photochemical and photophysical processes.…”