Comparison of Linear Response Theory, Projected Initial Maximum Overlap Method, and Molecular Dynamics Based Vibronic Spectra: The Case of Methylene Blue

Simulation of optical spectra is essential to molecular characterization and, in many cases, critical for interpreting experimental spectra. The most common method for simulating vibronic absorption spectra relies on the geometry optimization and computation of normal modes for ground and excited states. In this report, we show that utilization of such a procedure within an adiabatic linear response theory framework may lead to state mixings and a breakdown of the Born-Oppenheimer approximation, resulting in a poor description of absorption spectra. In contrast, computing excited states via a self-consistent eld method in conjunction with a maximum overlap model produces states that are not subject to such mixings. We show that this latter method produces vibronic spectra much more aligned with vertical excitation procedures, such as those computed from a vertical gradient or molecular dynamics trajectory-based approach. For the methylene blue chromophore, we compare vibronic absorption spectra computed with: an adiabatic Hessian approach with linear response theory optimized structures and normal modes, a vertical gradient procedure, the Hessian and normal modes of maximum overlap method optimized structures, and excitation energy time correlation functions generated from a molecular dynamics trajectory. Due to mixing between the bright S1 and dark S2 surfaces near the S1 minimum, computing the adiabatic Hessian with linear response theory time-dependent density functional theory with the B3LYP density functional predicts a large vibronic shoulder for the absorption spectrum that is not present for any of the other methods. Spectral densities are analyzed and we compare the behavior of the key normal mode that in linear response theory strongly couples to the optical excitation while showing S1/ S2 state mixings. Overall, our study provides a note of caution in computing vibronic spectra using the excited state adiabatic Hessian of linear response theory optimized structures and also showcases three alternatives that are not as subject to adiabatic state mixing effects.

Nonadiabatic Absorption Spectra and Ultrafast Dynamics of DNA and RNA Photoexcited Nucleobases

We have recently proposed a protocol for Quantum Dynamics (QD) calculations, which is based on a parameterisation of Linear Vibronic Coupling (LVC) Hamiltonians with Time Dependent (TD) Density Functional Theory (TD-DFT), and exploits the latest developments in multiconfigurational TD-Hartree methods for an effective wave packet propagation. In this contribution we explore the potentialities of this approach to compute nonadiabatic vibronic spectra and ultrafast dynamics, by applying it to the five nucleobases present in DNA and RNA. For all of them we computed the absorption spectra and the dynamics of ultrafast internal conversion (100 fs timescale), fully coupling the first 2–3 bright states and all the close by dark states, for a total of 6–9 states, and including all the normal coordinates. We adopted two different functionals, CAM-B3LYP and PBE0, and tested the effect of the basis set. Computed spectra are in good agreement with the available experimental data, remarkably improving over pure electronic computations, but also with respect to vibronic spectra obtained neglecting inter-state couplings. Our QD simulations indicate an effective population transfer from the lowest energy bright excited states to the close-lying dark excited states for uracil, thymine and adenine. Dynamics from higher-energy states show an ultrafast depopulation toward the more stable ones. The proposed protocol is sufficiently general and automatic to promise to become useful for widespread applications.