Computing linear optical spectra in the presence of nonadiabatic effects on graphics processing units using molecular dynamics and tensor-network approaches.

We compare two recently developed strategies, implemented in open source software packages, for computing linear optical spectra in condensed phase environments in the presence of nonadiabatic effects. Both approaches rely on computing excitation energy and transition dipole fluctuations along molecular dynamics (MD) trajectories, treating molecular and environmental degrees of freedom on the same footing. Spectra are then generated in two ways: in the recently developed Gaussian non-Condon theory, the linear response functions are computed in terms of independent adiabatic excited states, with non-Condon effects described through spectral densities of transition dipole fluctuations.

Environmentally Driven Symmetry Breaking Quenches Dual Fluorescence in Proflavine.

Nonadiabatic couplings between several electronic excited states are ubiquitous in many organic chromophores and can significantly influence optical properties. A recent experimental study demonstrated that the proflavine molecule exhibits surprising dual fluorescence in the gas phase, which is suppressed in polar solvent environments. Here, we uncover the origin of this phenomenon by parametrizing a linear-vibronic coupling Hamiltonian from spectral densities of system-bath coupling constructed along molecular dynamics trajectories, fully accounting for interactions with the condensed-phase environment.

Beyond the Condon limit: Condensed phase optical spectra from atomistic simulations.

While dark transitions made bright by molecular motions determine the optoelectronic properties of many materials, simulating such non-Condon effects in condensed phase spectroscopy remains a fundamental challenge. We derive a Gaussian theory to predict and analyze condensed phase optical spectra beyond the Condon limit. Our theory introduces novel quantities that encode how nuclear motions modulate the energy gap and transition dipole of electronic transitions in the form of spectral densities.