Finite-Temperature TD-DMRG for the Carrier Mobility of Organic Semiconductors.

A large number of nonadiabatic dynamical studies have been applied to reveal the nature of carrier transport in organic semiconductors with different approximations. We present here a "nearly exact" graphical-process-unit-based finite-temperature time-dependent density matrix renormalization group (TD-DMRG) method to evaluate the carrier mobility in organic semiconductors, as described by the electron-phonon model, in particular, in rubrene crystal, one of the prototypical organic semiconductors, with parameters derived from first-principles. We find that (i) TD-DMRG is a general and robust method that can bridge the gap between hopping and band pictures, covering a wide range of electronic coupling strengths and (ii) with realistic parameters, TD-DMRG is able to account for the experimentally observed "band-like" transport behavior (∂μ/∂T < 0) in rubrene. We further study the long-standing puzzle of the isotope effect for charge transport and unambiguously demonstrate that the negative isotope effect (∂μ/∂m < 0 where m is the atomic mass) should be universal.