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For simulations of strong field ionization using time-dependent configuration with a complex absorbing potential (TDCI-CAP), standard molecular basis set must be augmented by several sets of diffuse functions to support the wavefunction as it is distorted by the strong field and interacts with the absorbing potential. Various sets of diffuse functions used in previous studies have been extended and evaluated for their ability to model the angular dependence of strong field ionization. These sets include diffuse s, p, d and f gaussian functions with selected even-tempered exponents of the form 0.0001×2n placed on each atom. For single-centered test cases, the largest contribution to the ionization rate is from functions with a maximum in the radial distribution close to the onset of the complex absorbing potential, while functions with smaller exponents also contributed to the rate. For molecules, diffuse functions on adjacent centers overlap strongly, leading to linear dependencies. The transformation to remove these linear dependencies mixes functions of different angular momenta making it difficult to assess the importance of individual s, p, d and f functions in simulating the rate for molecules. As an alternative, a hierarchy of diffuse basis sets was constructed starting with a small set and adding one or two functions at a time. These basis sets were evaluated for their ability to reproduce the rate and the shape of the angular dependence of strong field ionization. When combined with the aug-cc-pVTZ molecular basis set and an absorbing potential starting at 3.5 times the van der Waals radius for each atom, the most diffuse s, p, d and f functions need to have exponents of 0.0032, 0.0032, 0.0064 and 0.0064, respectively, or smaller. Strong field ionization from electronegative atoms such as oxygen required additional f functions with tight exponents of 0.0512 and 0.1024. Diffuse basis sets that perform well for the angular dependence of the ionization rate with a static field are equally effective for strong field ionization with a linearly polarized 7 cycle 800 nm pulse. 

Modeling charge migration resulting from the coherent superposition of cation ground and excited states requires information about the potential energy surfaces of the relevant cation states. Since these states are often of the same electronic symmetry as the ground state of the cation, conventional single reference methods such as coupled cluster cannot be used for the excited states. The EOMCCSD-IP (equation of motion coupled cluster with single and double excitations and ionization) is a convenient and reliable “black-box” method that can be used for the ground and excited states of cations, yielding results of CCSD (coupled cluster with singles and double excitation) quality. Charge migration in haloacetylene cations arises from the superposition of the X and A states of HCCX+ (X = F, Cl, Br and I). The geometries, ionization potentials and vibrational frequencies have been calculated by CCSD/cc-pVTZ for neutral HCCX and the X state of HCCX+ and by EOM CCSD-IP/cc-pVTZ for the X and A states of HCCX+. The results agree very well with each other and with experiment. The very good agreement between CCSD and EOMCCSD-IP for the X states demonstrates that EOMCCSD-IP is a suitable method for calculating the structure and properties of ground and excited states for the HCCX cations. 

Strong field ionization of molecules by intense laser pulses can be simulated by time-dependent configuration interaction (TD-CI) with a complex absorbing potential (CAP). Standard molecular basis sets need to be augmented with several sets of diffuse functions for effective interaction with the CAP. This dramatically increases the number of configurations and the cost of the TD-CI simulations as the size of the molecules increases. The cost can be reduced by making use of spin symmetry and by employing an orbital energy cut-off to limit the number of virtual orbitals used to construct the excited configurations. Greater reductions in the number of virtual orbitals can be obtained by examining their interaction with the absorbing potential during simulations and their contributions to the strong field ionization rate. This can be determined from the matrix elements of the absorbing potential and the TD-CI coefficients from test simulations. Compared to a simple 3 hartree cut-off in the orbital energies, these approaches reduce the number of virtual orbitals by 20% - 35% for neutral molecules and 5%-10% for cations. As a result, the cost of simulations is reduced by 35% - 60% for neutral molecules and 5% - 10% for cations. The number of virtual orbitals needed can also be estimated by second-order perturbation theory without the need for test simulations. The number of virtual orbitals can be reduced further by adapting orbitals to the laser field using natural orbitals derived from test simulations. This is particularly effective for cations, yielding reductions of more than 20%. 

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?