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

Abstract

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.

Photoelectron spectra of 2-thiouracil, 4-thiouracil, and 2,4-dithiouracil

“…The generation of photoelectron spectra has been performed using tools from the development version of the Sharc molecular dynamics suite. [46][47][48] …”

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

“…10 Trajectory surface hopping (TSH), which approximates the dynamics of a nuclear wavepacket by a swarm of independent classical trajectories, has also been modified to incorporate SOC effects. [11][12][13][14][15] Freedom in the choice of different spin representations [11][12][13][14]16 or hopping schemes 17 has resulted in a plethora of TSH algorithms, which are, however, prone to shortcomings of the independent trajectory approximation. 18,19 In particular, the spin-diabatic representation for including SOC in TSH has been questioned due to a lack of rotational invariance for electronic population dynamics.…”

Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces

“…These regions are even more difficult to treat and thus many developments are present in the literature [76][77][78][79][80][81][82]. The González group gives an example of deactivation of 5-bromouracil after UV excitation by using their own development of surface-hopping dynamics to deal with intersystem crossing regions, which are found from multi-reference wave function calculations [83,84].…”