Full-dimensional treatment of short-time vibronic dynamics in molecular high-harmonics generation process in methane

We present derivation and implementation of the Multi-Configurational Strong-Field Approximation with Gaussian nuclear Wave Packets (MC-SFA-GWP) -- a version of the molecular strong-field approximation which treats all electronic and nuclear degrees of freedom, including their correlations, quantum-mechanically. The technique allows, for the first time, realistic simulation of high-harmonic emission in polyatomic molecules without invoking reduced-dimensionality models for the nuclear motion or the electronic structure. We use MC-SFA-GWP to model isotope effects in high-harmonics generation (HHG) spectroscopy of methane. The HHG emission in this molecule transiently involves strongly vibronically-coupled $^2F_2$ electronic state of the $\rm CH_4^+$ cation. We show that the isotopic HHG ratio in methane contains signatures of: a) field-free vibronic dynamics at the conical intersection (CI); b) resonant features in the recombination cross-sections; c) laser-driven bound-state dynamics; as well as d) the well-known short-time Gaussian decay of the emission. We assign the intrinsic vibronic feature (a) to a relatively long-lived ($\ge4$ fs) vibronic wave packet of the singly-excited $\nu_4$ ($t_2$) and $\nu_2$ ($e$) vibrational modes, strongly coupled to the components of the $^2F_2$ electronic state. We demonstrate that these physical effects differ in their dependence on the wavelength, intensity, and duration of the driving pulse, allowing them to be disentangled. We thus show that HHG spectroscopy provides a versatile tool for exploring both conical intersections and resonant features in photorecombination matrix elements in the regime not easily accessible with other techniques

Grand-Canonical Quantized Liquid Density-Functional Theory in a Car-Parrinello Implementation

Quantized Liquid Density-Functional Theory [Phys. Rev. E 2009, 80, 031603], a method developed to assess the adsorption of gas molecules in porous nanomaterials, is reformulated within the grand canonical ensemble. With the grand potential it is possible to compare directly external and internal thermodynamic quantities. In our new implementation, the grand potential is minimized utilizing the Car-Parrinello approach and gives, in particular for low temperature simulations, a significant computational advantage over the original canonical approaches. The method is validated against original QLDFT, and applied to model potentials and graphite slit pores.Comment: 19 pages, 5 figure

One-Electron Ionization of Multielectron Systems in Strong Nonresonant Laser Fields

We present a novel approach to calculating strong field ionization dynamics of multielectron molecular targets. Adopting a multielectron wavefunction ansatz based on field-free ab initio neutral and ionic multielectron states, a set of coupled time-dependent single-particle Schroedinger equations describing the neutral amplitude and continuum electron are constructed. These equations, amenable to direct numerical solution or further analytical treatment, allow one to study multielectron effects during strong field ionization, recollision, and high harmonic generation. We apply the method to strong field ionization of CO_2, and suggest the importance of intermediate core excitation to explain previous failure of analytical models to reproduce experimental ionization yields for this molecule.Comment: 25 pages, 6 figure

Sequential and direct ionic excitation in the strong-field ionization of 1-butene molecules

We study the Strong-Field Ionization (SFI) of the hydrocarbon 1-butene as a function of wavelength using photoion-photoelectron covariance and coincidence spectroscopy. We observe a striking transition in the fragment-associated photoelectron spectra: from a single Above Threshold Ionization (ATI) progression for photon energies less than the cation D0–D1 gap to two ATI progressions for a photon energy greater than this gap. For the first case, electronically excited cations are created by SFI populating the ground cationic state D0, followed by sequential post-ionization excitation. For the second case, direct sub-cycle SFI to the D1 excited cation state contributes significantly. Our experiments access ionization dynamics in a regime where strong-field and resonance-enhanced processes can interplay

Laser-induced interference, focusing, and diffraction of rescattering molecular photoelectrons

We solve the time-dependent Schrodinger equation in three dimensions for H-2(+) in a one-cycle laser pulse of moderate intensity. We consider fixed nuclear positions and Coulomb electron-nuclear interaction potentials. We analyze the field-induced electron interference and diffraction patterns. To extract the ionization dynamics we subtract the excitations to low-lying bound states explicitly. We follow the time evolution of a well-defined wave packet that is formed near the first peak of the laser field. We observe the fragmentation of the wave packet due to molecular focusing. We show how to retrieve a diffraction molecular image by taking the ratio of the momentum distributions in the two lateral directions. The positions of the diffraction peaks are well described by the classical double slit diffraction rule