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.