The BOMD simulations of TPA crystals were performed at 70, 100, 200 and 300 K using a canonical sampling through velocity rescaling (CSVR) thermostat as implemented in the CP2K package. In order to study the effect of NQE, we have performed PIMD simulations at the same temperatures. These simulations were carried out using the i-PI 64 and CP2K software, where i-PI propagates the nuclear motion and CP2K calculates the electronic forces and energy. A coloured noise Generalised Langevin Equation based thermostat (GLE) is coupled to PIMD simulation (PIGLET) to accelerate the convergence with respect to the number of beads. The converged number of beads for the PIGLET simulation at 70 K was estimated to be 16 (the results of the convergence tests are shown in Section 2 of the Supporting Information (SI)). For the higher temperature simulations we have used, for consistency, the same number of beads. The parameters for the diffusion and drift matrices of the coloured noise thermostat were generated from the online repository ( ) such that the maximum physical frequency lie close to 4000 cm -1 for all temperatures. The equations of motion in the various molecular dynamics simulations were integrated with a time step of 0.5 fs. The BOMD and PIGLET simulations were performed for 35 ps and 20 ps respectively. The analysis were done using the last 30 ps and 18 ps of the BOMD and PIGLET trajectories respectively. of the Supporting Information showing consistency with previous reports. At this temperature, all the TPA molecules are in the trans configuration (Figure In this study, we refer to these intra chain DPT junctions throughout the crystals as the L-tautomer as shown in Figure