Controlling Electronic Coherences and the Curvature Induced by the Derivative Coupling at a Conical Intersection: A Quantum Ehrenfest (QuEh) Protocol for Reaction Path Following Application to "Channel 3" Benzene Photochemistry.

We report a protocol for the implementation of "reaction path following" from a transition state through a conical intersection, including both the path curvature induced by the derivative coupling and the corresponding induced electronic coherences. This protocol focuses on the "central" Gaussian wavepacket (initially unexcited) in the quantum Ehrenfest (QuEh) method. Like the reaction path following, the normal mode corresponding to the imaginary frequency at the transition state is given an initial momentum. The protocol is applied to the "channel 3" radiationless decay of benzene. We also demonstrate that one can enhance the effect of the derivative coupling and the electronic coherence with an IR pulse.

Prediction through quantum dynamics simulations: Photo-excited cyclobutanone.

Quantum dynamics simulations are becoming a standard tool for simulating photo-excited molecular systems involving a manifold of coupled states, known as non-adiabatic dynamics. While these simulations have had many successes in explaining experiments and giving details of non-adiabatic transitions, the question remains as to their predictive power. In this work, we present a set of quantum dynamics simulations on cyclobutanone using both grid-based multi-configuration time-dependent Hartree and direct dynamics variational multi-configuration Gaussian methods. The former used a parameterized vibronic coupling model Hamiltonian, and the latter generated the potential energy surfaces on the fly. The results give a picture of the non-adiabatic behavior of this molecule and were used to calculate the signal from a gas-phase ultrafast electron diffraction (GUED) experiment. Corresponding experimental results will be obtained and presented at a later stage for comparison to test the predictive power of the methods. The results show that over the first 500 fs after photo-excitation to the S2 state, cyclobutanone relaxes quickly to the S1 state, but only a small population relaxes further to the S0 state. No significant transfer of population to the triplet manifold is found. It is predicted that the GUED experiments over this time scale will see signals related mostly to the C-O stretch motion and elongation of the molecular ring along the C-C-O axis.

Unraveling the Ultrafast Photochemical Dynamics of Nitrobenzene in Aqueous Solution.

Nitroaromatic compounds are major constituents of the brown carbon aerosol particles in the troposphere that absorb near-ultraviolet (UV) and visible solar radiation and have a profound effect on the Earth's climate. The primary sources of brown carbon include biomass burning, forest fires, and residential burning of biofuels, and an important secondary source is photochemistry in aqueous cloud and fog droplets. Nitrobenzene is the smallest nitroaromatic molecule and a model for the photochemical behavior of larger nitroaromatic compounds. Despite the obvious importance of its droplet photochemistry to the atmospheric environment, there have not been any detailed studies of the ultrafast photochemical dynamics of nitrobenzene in aqueous solution. Here, we combine femtosecond transient absorption spectroscopy, time-resolved infrared spectroscopy, and quantum chemistry calculations to investigate the primary steps following the near-UV (λ ≥ 340 nm) photoexcitation of aqueous nitrobenzene. To understand the role of the surrounding water molecules in the photochemical dynamics of nitrobenzene, we compare the results of these investigations with analogous measurements in solutions of methanol, acetonitrile, and cyclohexane. We find that vibrational energy transfer to the aqueous environment quenches internal excitation, and therefore, unlike the gas phase, we do not observe any evidence for formation of photoproducts on timescales up to 500 ns. We also find that hydrogen bonding between nitrobenzene and surrounding water molecules slows the S1/S0 internal conversion process.

A First Proposal on the Nitrobenzene Photorelease Mechanism of NO2 and Its Relation to NO Formation through a Roaming Mechanism.

Despite the fact that NO2 is considered to be the main photoproduct of nitrobenzene photochemistry, no mechanism has ever been proposed to rationalize its formation. NO photorelease is instead a more studied process, probably due to its application in the drug delivery sector and the study of roaming mechanisms. In this contribution, a photoinduced mechanism accounting for the formation of NO2 in nitrobenzene is theorized based on CASPT2, CASSCF, and DFT electronic structure calculations and CASSCF classical dynamics. A triplet nπ* state is shown to evolve toward C-NO2 dissociation, being, in fact, the only low-lying excited state favoring such a deformation. Along the triplet dissociation path, the possibility to decay to the singlet ground state results in the frustration of the dissociation and in the recombination of the fragments, either back to the nitro or the nitrite isomer. The thermal decomposition of the latter to NO constitutes globally a roaming mechanism of NO formation.

Quantum dynamics of excited state proton transfer in green fluorescent protein.

Photoexcitation of green fluorescent protein (GFP) triggers long-range proton transfer along a "wire" of neighboring protein residues, which, in turn, activates its characteristic green fluorescence. The GFP proton wire is one of the simplest, most well-characterized models of biological proton transfer but remains challenging to simulate due to the sensitivity of its energetics to the surrounding protein conformation and the possibility of non-classical behavior associated with the movement of lightweight protons. Using a direct dynamics variational multiconfigurational Gaussian wavepacket method to provide a fully quantum description of both electrons and nuclei, we explore the mechanism of excited state proton transfer in a high-dimensional model of the GFP chromophore cluster over the first two picoseconds following excitation. During our simulation, we observe the sequential starts of two of the three proton transfers along the wire, confirming the predictions of previous studies that the overall process starts from the end of the wire furthest from the fluorescent chromophore and proceeds in a concerted but asynchronous manner. Furthermore, by comparing the full quantum dynamics to a set of classical trajectories, we provide unambiguous evidence that tunneling plays a critical role in facilitating the leading proton transfer.

On the multiphoton ionisation photoelectron spectra of phenol.

The phenol molecule is a prototype for non-adiabatic dynamics and the excited-state photochemistry of biomolecules. In this article, we report a joint theoretical and experimental investigation on the resonance enhanced multiphoton ionisation photoelectron (REMPI) spectra of the two lowest ionisation bands of phenol. The focus is on the theoretical interpretation of the measured spectra using quantum dynamics simulations. These were performed by numerically solving the time-dependent Schrödinger equation using the multi-layer variant of the multiconfiguration time-dependent Hartree algorithm together with a vibronic coupling Hamiltonian model. The ionising laser pulse is modelled explicitly within the ionisation continuum model to simulate experimental femtosecond 1+1 REMPI photoelectron spectra. These measured spectra are sensitive to very short lived electronically excited states, providing a rigorous benchmark for our theoretical methods. The match between experiment and theory allows for an interpretation of the features of the spectra at different wavelengths and shows that there are features due to both 'direct' and 'indirect' ionisation, resulting from non-resonant and resonant excitation by the pump pulse.

Benchmarking non-adiabatic quantum dynamics using the molecular Tully models.

On-the-fly non-adiabatic dynamics methods are becoming more important as tools to characterise the time evolution of a system after absorbing light. These methods, which calculate quantities such as state energies, gradients and interstate couplings at every time step, circumvent the requirement for pre-computed potential energy surfaces. There are a number of different algorithms used, the most common being Tully Surface Hopping (TSH), but all are approximate solutions to the time-dependent Schrödinger equation and benchmarking is required to understand their accuracy and performance. For this, a common set of systems and observables are required to compare them. In this work, we validate the on-the-fly direct dynamics variational multi-configuration Gaussian (DD-vMCG) method using three molecular systems recently suggested by Ibele and Curchod as molecular versions of the Tully model systems used to test one-dimensional non-adiabatic behaviour [Ibele et al., Phys. Chem. Chem. Phys. 2020, 22, 15183-15196]. Parametrised linear vibronic potential energy surfaces for each of the systems were also tested and compared to on-the-fly results. The molecules, which we term the Ibele-Curchod models, are ethene, DMABN and fulvene and the authors used them to test and compare several versions of the Ab Initio Multiple Spawning (AIMS) method alongside TSH. The three systems present different deactivation pathways after excitation to their ππ* bright states. When comparing DD-vMCG to AIMS and TSH, we obtain crucial differences in some cases, for which an explanation is provided by the classical nature and the chosen initial conditions of the TSH simulations.