Predicting kinetics of spin-dependent reactions in an external magnetic field with nonadiabatic statistical theory.

We introduce a theoretical framework to study the kinetics of the chemical reactions involving transitions between electronic states with different spin quantum numbers in an external magnetic field. The new equations for calculating transition probabilities and rate constants are used to generalize the nonadiabatic statistical theory, which now accounts for both the spin-orbit and Zeeman couplings between electronic states. Focusing on the singlet-triplet transitions, we define two dimensionless parameters to characterize (1) the magnetic field strength relative to the strength of spin-orbit coupling and (2) the relative magnitudes of the spin-orbit coupling matrix elements that couple the singlet state to different components of the triplet state.

Predicting Kinetics and Dynamics of Spin-Dependent Processes.

ConspectusPredicting mechanisms and rates of nonadiabatic spin-dependent processes including photoinduced intersystem crossings, thermally activated spin-forbidden reactions, and spin crossovers in metal centers is a very active field of research. These processes play critical roles in transition-metal-based and metalloenzymatic catalysis, molecular magnets, light-harvesting materials, organic light-emitting diodes, photosensitizers for photodynamic therapy, and many other applications. Therefore, accurate modeling of spin-dependent processes in complex systems and on different time scales is important for many problems in chemistry, biochemistry, and materials sciences.

NAST: Nonadiabatic Statistical Theory Package for Predicting Kinetics of Spin-Dependent Processes.

We present a nonadiabatic statistical theory (NAST) package for predicting kinetics of spin-dependent processes, such as intersystem crossings, spin-forbidden unimolecular reactions, and spin crossovers. The NAST package can calculate the probabilities and rates of transitions between the electronic states of different spin multiplicities. Both the microcanonical (energy-dependent) and canonical (temperature-dependent) rate constants can be obtained.

Complementary version of fermion coupled coherent states method and gram-schmidt algorithm: Theory and applications for electronic states of H2 and H2.

In our previous report, we introduced a new version of Fermion coupled coherent states method (FCCS) which was especially suited for simulating the first symmetric spatial electronic state of two-electron systems. In this manuscript, we report a complementary version for FCCS method to simulate both of the first symmetric and antisymmetric spatial electronic states of two-electron systems. Moreover, the Gram-Schmidt orthogonalization process is employed to reach the excited states of the system.