Daniel Keefer

Conical intersections (CIs) play a crucial role in determining the photochemical outcomes of excited-state molecular dynamics. Such is the case for systems such as furan and many of its derivatives, which exhibit two main competing pathways—ring-opening and ring-puckering that are mediated by two distinct CIs. Since even single CIs are hard to detect spectroscopically, disentangling the contribution between multiple competing CIs is an exceptionally difficult challenge. In this study, we theoretically evaluate the possibility to disentangle competing CI-mediated pathways in 2,5-dichlorofuran with ultrafast electron diffraction (UED). We simulate the photochemistry of 2,5-dichlorofuran with semi-classical surface-hopping molecular dynamics based on XMS-CASPT2 theory. This approach captures non-adiabatic transitions between electronic states at CIs. Compared to furan, we find that chlorine substitution pushes the relaxation time well above 100 fs, which is beneficial for current temporal resolution in UED. We simulate UED patterns that involve scattering off electronic and nuclear charge densities, thereby being sensitive to structural changes in the molecule. In the static UED patterns of the optimized conical intersection structures, we find an observable difference between puckering and opening. The pair distribution functions of the UED signals we calculated exhibit signature peaks of the opening CI at 6.1 Å and of the puckering CI at 3.7 Å. Because the trajectories primarily exhibit mixed puckering/opening character instead of a clean branching, these differences are not clearly visible in the ensemble UED pattern.

Accessing coherences is key to fully understand and control ultrafast dynamics of complex quantum systems like molecules. Most photochemical processes are mediated by conical intersections, which generate coherences between electronic states in molecules. We show with accurate calculations performed on gas-phase methyl iodide that electronic coherences of spin-orbit-split states persist in atomic iodine after dissociation. Our simulation predicts a maximum magnitude of vibronic coherence in the molecular regime of 0.75% of the initially photoexcited state population. Upon dissociation, one-third of this coherence magnitude is transferred to a long-lived atomic coherence where vibrational decoherence can no longer occur. To trace these dynamics, we propose a tabletop experimental approach—heterodyned attosecond four-wave-mixing spectroscopy. This technique can temporally resolve small electronic coherence magnitudes and reconstruct the full complex coherence function via phase cycling. Hence, heterodyned attosecond four-wave-mixing spectroscopy leads the way to a complete understanding and optimal control of spin-orbit-coupled electronic states in photochemistry.

We propose an X-ray Raman pump-X-ray diffraction probe scheme to follow solvation dynamics upon charge migration in a solute molecule. The X-ray Raman pump selectively prepares a valence electronic wavepacket in the solute, while the probe provides information about the entire molecular ensemble. A combination of molecular dynamics and ab initio quantum chemistry simulations is applied to a Zn-Ni porphyrin dimer in water. Using time-resolved X-ray diffraction and pair distribution functions, we extracted solvation shell dynamics.

We study the ultrafast time evolution of cyclobutanone excited to the singlet n → Rydberg state through non-adiabatic surface-hopping simulationsperformed at extended multi-state complete active space second-order perturbation (XMS-CASPT2) level of theory. These dynamics predict relaxation to the ground-state with a timescale of 822 ± 45 fs with minimal involvement of the triplets. The major relaxation path to the ground-state involves a three-state degeneracy region and leads to a variety of fragmented photoproducts. We simulate the resulting time-resolved electron-diffraction spectra, which track the relaxation of the excited state and the formation of various photoproducts in the ground state.

Elementary events that determine photochemical outcomes and molecular functionalities happen on the femtosecond and subfemtosecond timescales. Among the most ubiquitous events are the nonadiabatic dynamics taking place at conical intersections. These facilitate ultrafast, nonradiative transitions between electronic states in molecules that can outcompete slower relaxation mechanisms such as fluorescence. The rise of ultrafast X-ray sources, which provide intense light pulses with ever-shorter durations and larger observation bandwidths, has fundamentally revolutionized our spectroscopic capabilities to detect conical intersections. Recent theoretical studies have demonstrated an entirely new signature emerging once a molecule traverses a conical intersection, giving detailed insights into the coupled nuclear and electronic motions that underlie, facilitate, and ultimately determine the ultrafast molecular dynamics. Following a summary of current sources and experiments, we survey these techniques and provide a unified overview of their capabilities. We discuss their potential to dramatically increase our understanding of ultrafast photochemistry.

Understanding conical intersection (CI) dynamics and subsequent conformational changes is key for exploring and controlling photo-reactions in aromatic molecules. Monitoring of their time-resolved dynamics remains a formidable experimental challenge. In this study, we simulate the photoinduced S₃ to S₁ non-adiabatic dynamics of cyclooctatetraene (COT), involving multiple CIs with relaxation times in good agreement with experiment. We further investigate the possibility to directly probe the CI passages in COT by off-resonant X-ray Raman spectroscopy (TRUECARS) and time-resolved X-ray diffraction (TRXD). We find that these signals sensitively monitor key chemical features during the ultrafast dynamics. First, we distinguish two CIs by TRUECARS signals with their appearances at different Raman shift. Second, we demonstrate that TRXD, where X-ray photons scatter off electron densities, can resolve ultrafast changes in the aromaticity of COT. It can further distinguish between planar and non-planar geometries explored during the dynamics, as e.g. two different tetraradical-type CIs. The knowledge gained from these measurements can give unique insight into fundamental chemical properties that dynamically change during non-adiabatic passages.

Recent development of X-ray free-electron lasers and megaelectronvolt radio-frequency electron guns have made ultrafast X-ray and electron diffraction measurements possible, thereby capturing chemical dynamics with atomic-spatial and femtosecond-temporal resolutions. We present a unified formulation of standard homodyne-detected and heterodyne-detected signals for both techniques. Noting that X-rays scatter from molecular electrons while electrons scatter from both molecular electrons and nuclei, we show how the two diffraction signals can be combined to reveal novel chemical information that is unavailable by solely using each technique alone. By subtracting the homodyne-detected X-ray and electron diffraction signals, a mixed electronic-nuclear interference in electron diffraction can be identified with a self-heterodyne nature for the direct imaging of attosecond electron dynamics where the scattering off molecular nuclei serves as a local oscillator for the scattering off molecular electrons. By subtracting heterodyne-detected X-ray and electron diffraction, the purely nuclear charge density can be singled out.

The ultrafast photoinduced chirality loss of 2-iodobutane is studied theoretically by time- and frequency-resolved X-ray circular dichroism (TRXCD) spectroscopy. Following an optical excitation, the iodine atom dissociates from the chiral center, which we capture by quantum non-adiabatic molecular dynamics simulations. At variable time delays after the pump, the resonant X-ray pulse selectively probes the iodine and carbon atom involved in the chiral dissociation through a selected core-to-valence transition. The TRXCD signal at the iodine L₁ edge accurately captures the timing of C-I photodissociation and thereby chirality loss, c.a 70 fs. The strong electric dipole-electric quadrupole (ED-EQ) response makes this signal particularly sensitive to vibronic coherence at the high X-ray regime. At the carbon K-edges, the signals monitor the molecular chirality of the 2-butyl radical photoproduct and the spin state of the iodine atom. The ED-EQ response is masked under the strong electric dipole-magnetic dipole response, making this signal intuitive for the electronic population. The evolution of the core electronic states and its chiral sensitivity is discussed. Overall, the element-specific TRXCD signal provides a detailed picture of molecular dynamics and offers a unique sensitive window into the time-dependent chirality of molecules.