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Abstract Conical intersections between electronic states often dictate the chemistry of photoexcited molecules. Recently developed sources of ultrashort extreme ultraviolet (XUV) pulses tuned to element-specific transitions in molecules allow for the unambiguous detection of electronic state-switching at a conical intersection. Here, the fragmentation of photoexcitediso-propyl iodide andtert-butyl iodide molecules (i-C₃H₇I andt-C₄H₉I) through a conical intersection between³Q₀/¹Q₁spin–orbit states is revealed by ultrafast XUV transient absorption measuring iodine 4dcore-to-valence transitions. The electronic state-sensitivity of the technique allows for a complete mapping of molecular dissociation from photoexcitation to photoproducts. In both molecules, the sub-100 fs transfer of a photoexcited wave packet from the³Q₀state into the¹Q₁state at the conical intersection is captured. The results show how differences in the electronic state-switching of the wave packet ini-C₃H₇I andt-C₄H₉I directly lead to differences in the photoproduct branching ratio of the two systems. 

Abstract Attosecond probing of core-level electronic transitions provides a sensitive tool for studying valence molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy to follow the valence dynamics of strong-field initiated processes in methyl bromide. By probing the 3dcore-to-valence transition, we resolve the strong field excitation and ensuing fragmentation of the neutral σ* excited states of methyl bromide. The results provide a clear signature of the non-adiabatic passage of the excited state wavepacket through a conical intersection. We additionally observe competing, strong field initiated processes arising in both the ground state and ionized molecule corresponding to vibrational and spin-orbit motion, respectively. The demonstrated ability to resolve simultaneous dynamics with few-femtosecond resolution presents a clear path forward in the implementation of attosecond XUV spectroscopy as a general tool for probing competing and complex molecular phenomena with unmatched temporal resolution. 

The photodissociation dynamics of alkyl iodides along the C–I bond are captured by attosecond extreme-ultraviolet (XUV) transient absorption spectroscopy employing resonant ∼20 fs UV pump pulses. The methodology of previous experiments on CH₃I [Chang et al., J. Chem. Phys. 154, 234301 (2021)] is extended to the investigation of a C–I bond-breaking reaction in the dissociative A-band of C₂H₅I, i-C₃H₇I, and t-C₄H₉I. Probing iodine 4 d core-to-valence transitions in the XUV enables one to map wave packet bifurcation at a conical intersection in the A-band as well as coherent vibrations in the ground state of the parent molecules. Analysis of spectroscopic bifurcation signatures yields conical intersection crossing times of 15 ± 4 fs for CH₃I, 14 ± 5 fs for C₂H₅I, and 24 ± 4 fs for i-C₃H₇I and t-C₄H₉I, respectively. Observations of coherent vibrations, resulting from a projection of A-band structural dynamics onto the ground state by resonant impulsive stimulated Raman scattering, indirectly reveal multimode C–I stretch and CCI bend vibrations in the A-bands of C₂H₅I, i-C₃H₇I, and t-C₄H₉I. 

We theoretically investigate the role of complex dipole phase in the attosecond probing of charge migration. The iodobromoacetylene ion (ICCBr⁺) is considered as an example, in which one can probe charge migration by accessing both the iodine and bromine ends of the molecule with different spectral windows of an extreme-ultraviolet (XUV) pulse. The analytical expression for transient absorption shows that the site-specific information of charge migration is encoded in the complex phase of cross dipole products for XUV transitions between the I-4dand Br-3dspectral windows. Ab-initio quantum chemistry calculations on ICCBr⁺reveal that there is a constantπphase difference between the I-4dand Br-3dtransient-absorption spectral windows, irrespective of the fine-structure energy splittings. Transient absorption spectra are simulated with a multistate model including the complex dipole phase, and the results correctly reconstruct the charge-migration dynamics via the quantum beats in the two element spectral windows, exhibiting out-of-phase oscillations. 

Attosecond extreme ultraviolet (XUV) and soft x-ray sources provide powerful new tools for studying ultrafast molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy (ATAS) to follow strong-field-initiated dynamics in vinyl bromide. Probing the Br M edge allows one to assess the competing processes in neutral and ionized molecular species. Using ab initio non-adiabatic molecular dynamics, we simulate the neutral and cationic dynamics resulting from the interaction of the molecule with the strong field. Based on the dynamics results, the corresponding time-dependent XUV transient absorption spectra are calculated by applying high-level multi-reference methods. The state-resolved analysis obtained through the simulated dynamics and related spectral contributions enables a detailed and quantitative comparison with the experimental data. The main outcome of the interaction with the strong field is unambiguously the population of the first three cationic states, D1, D2, and D3. The first two show exclusively vibrational dynamics while the D3 state is characterized by an ultrafast dissociation of the molecule via C–Br bond rupture within 100 fs in 50% of the analyzed trajectories. The combination of the three simulated ionic transient absorption spectra is in excellent agreement with the experimental results. This work establishes ATAS in combination with high-level multi-reference simulations as a spectroscopic technique capable of resolving coupled non-adiabatic electronic-nuclear dynamics in photoexcited molecules with sub-femtosecond resolution. 

Abstract The removal of electrons located in the core shells of molecules creates transient states that live between a few femtoseconds to attoseconds. Owing to these short lifetimes, time-resolved studies of these states are challenging and complex molecular dynamics driven solely by electronic correlation are difficult to observe. Here, we obtain few-femtosecond core-excited state lifetimes of iodine monochloride by using attosecond transient absorption on iodine 4 d −1 6 p transitions around 55 eV. Core-level ligand field splitting allows direct access of excited states aligned along and perpendicular to the ICl molecular axis. Lifetimes of 3.5 ± 0.4 fs and 4.3 ± 0.4 fs are obtained for core-hole states parallel to the bond and 6.5 ± 0.6 fs and 6.9 ± 0.6 fs for perpendicular states, while nuclear motion is essentially frozen on this timescale. Theory shows that the dramatic decrease of lifetime for core-vacancies parallel to the covalent bond is a manifestation of non-local interactions with the neighboring Cl atom of ICl.