Ab Initio Linear and Pump-Probe Spectroscopy of Excitons in Molecular Crystals

Linear and nonlinear spectroscopies are powerful tools used to investigate the energetics and dynamics of electronic excited states of both molecules and crystals. While highly accurate ab initio calculations of molecular spectra can be performed relatively routinely, extending these calculations to periodic systems is challenging. Here, we present calculations of the linear absorption spectrum and pump-probe two-photon photoemission spectra of the naphthalene crystal using equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD). Molecular acene crystals are of interest due to the low-energy multiexciton singlet states they exhibit, which have been studied extensively as intermediates involved in singlet fission. Our linear absorption spectrum is in good agreement with experiment, predicting a first exciton absorption peak at 4.4 eV, and our two-photon photoemission spectra capture the qualitative behavior of multiexciton states, whose double-excitation character cannot be captured by current methods. The simulated pump-probe spectra provide support for existing interpretations of two-photon photoemission experiments in closely related acene crystals such as tetracene and pentacene.