Quantum vibronic effects on the electronic properties of molecular
crystals
- URL: http://arxiv.org/abs/2304.13687v1
- Date: Wed, 26 Apr 2023 17:13:14 GMT
- Title: Quantum vibronic effects on the electronic properties of molecular
crystals
- Authors: Arpan Kundu and Giulia Galli
- Abstract summary: We consider a system composed of relatively rigid molecules, a diamondoid crystal, and one composed of floppier molecules, NAI-DMAC.
We compute fundamental electronic gaps at the DFT level of theory, with the PBE and SCAN functionals, by coupling first-principles molecular dynamics with a nuclear quantum thermostat.
- Score: 0.0
- License: http://arxiv.org/licenses/nonexclusive-distrib/1.0/
- Abstract: We present a study of molecular crystals, focused on the effect of nuclear
quantum motion and anharmonicity on their electronic properties. We consider a
system composed of relatively rigid molecules, a diamondoid crystal, and one
composed of floppier molecules, NAI-DMAC, a thermally activated delayed
fluorescence compound. We compute fundamental electronic gaps at the DFT level
of theory, with the PBE and SCAN functionals, by coupling first-principles
molecular dynamics with a nuclear quantum thermostat. We find a sizable
zero-point-renormalization (ZPR) of the band gaps, which is much larger in the
case of diamondoids (~ 0.6 eV) than for NAI-DMAC (~ 0.22 eV). We show that the
frozen phonon (FP) approximation, which neglects inter-molecular anharmonic
effects, leads to a large error (~ 50%) in the calculation of the band gap ZPR.
Instead, when using a stochastic method, we obtain results in good agreement
with those of our quantum simulations for the diamondoid crystal. However, the
agreement is worse for NAI-DMAC where intra-molecular anharmonicities
contribute to the ZPR. Our results highlight the importance of accurately
including nuclear and anharmonic quantum effects to predict the electronic
properties of molecular crystals.
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