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Abstract Identifying the short-lived intermediates and reaction mechanisms of multi-channel radical cation fragmentation processes remains a current and important challenge to understanding and predicting mass spectra. We find that coherent oscillations in the femtosecond time-dependent yields of several product ions following ultrafast strong-field ionization represent spectroscopic signatures that elucidate their mechanism of formation and identify the intermediate(s) they originate from. Experiments on endo-dicyclopentadiene show that vibrational frequencies from various intermediates are mapped onto their resulting products. Aided by ab initio methods, we identify the vibrational modes of both the cleaved and intact molecular ion intermediates. These results confirm stepwise and concerted fragmentation pathways of the dicyclopentadiene ion. This study highlights the power of tracking the femtosecond dynamics of all product ions simultaneously and sheds further light onto one of the fundamental reaction mechanisms in mass spectrometry, the retro-Diels Alder reaction. 

The exponential scaling of complete active space and full configuration interaction (CI) calculations limits the ability of quantum chemists to simulate the electronic structures of strongly correlated systems. Herein, we present corner hierarchically approximated CI (CHACI), an approach to wave function compression based on corner hierarchical matrices (CH-matrices)—a new variant of hierarchical matrices based on block-wise low-rank decomposition. By application to dodecacene, a strongly correlated molecule, we demonstrate that CH matrix compression provides superior compression compared to truncated global singular value decomposition. The compression ratio is shown to improve with increasing active space size. By comparison of several alternative schemes, we demonstrate that superior compression is achieved by (a) using a blocking approach that emphasizes the upper-left corner of the CI vector, (b) sorting the CI vector prior to compression, and (c) optimizing the rank of each block to maximize information density. 

Computer simulation has long been an essential partner of ultrafast experiments, allowing the assignment of microscopic mechanistic detail to low-dimensional spectroscopic data. However, the ability of theory to make a priori predictions of ultrafast experimental results is relatively untested. Herein, as a part of a community challenge, we attempt to predict the signal of an upcoming ultrafast photochemical experiment using state-of-the-art theory in the context of preexisting experimental data. Specifically, we employ ab initio Ehrenfest with collapse to a block mixed quantum–classical simulations to describe the real-time evolution of the electrons and nuclei of cyclobutanone following excitation to the 3s Rydberg state. The gas-phase ultrafast electron diffraction (GUED) signal is simulated for direct comparison to an upcoming experiment at the Stanford Linear Accelerator Laboratory. Following initial ring-opening, dissociation via two distinct channels is observed: the C3 dissociation channel, producing cyclopropane and CO, and the C2 channel, producing CH2CO and C2H4. Direct calculations of the GUED signal indicate how the ring-opened intermediate, the C2 products, and the C3 products can be discriminated in the GUED signal. We also report an a priori analysis of anticipated errors in our predictions: without knowledge of the experimental result, which features of the spectrum do we feel confident we have predicted correctly, and which might we have wrong? 

We report femtosecond time-resolved measurements of the McLa!erty rearrangement following the strong-field tunnel ionization of 2-pentanone, 4-methyl-2-pentanone, and 4,4-dimethyl-2-pentanone. The pump−probe-dependent yields of the McLa!erty product ion are fit to a biexponential function with fast ("100 fs) and slow ("10 ps) time constants, the latter of which is faster for the latter two compounds. Following nearly instantaneous ionization, the fast time scale is associated with rotation of the molecule to a six-membered cyclic intermediate that facilitates transfer of the !-hydrogen, while the "50−100 times longer time scale is associated with a "-bond rearrangement and bond cleavage between the #- and $-carbons to produce the enol cation. These experimental measurements are supported by ab initio molecular dynamics trajectories, which further confirm the time scale of this important stepwise reaction in mass spectrometry. 

We report a significant Stokes shift enhancement in near-infrared fluorescing cyanines as a result of C4′-substitution with cyclic or acyclic amines. Based on a combined experimental and density functional study, a simple strategy for optimizing the Stokes shift is proposed. By tuning the relative energies of cyanine-like and bis-dipolar conformers, differing in the rotational angle of the amine substituent, it is possible to develop molecules that undergo conformational change upon excitation, resulting in a predictable Stokes shift.