We report high-level calculations of the excited states of [2,2]-paracyclophane (PCP), which was recently investigated experimentally by ultrafast pump-probe experiments on oriented single crystals [Haggag et al., ChemPhotoChem 6 e202200181 (2022)]. PCP, in which the orientation of the two benzene rings and their range of motion are constrained, serves as a model for studying benzene exciplex formation. The character of the excimer state and the state responsible for the brightest transition are similar to those in benzene dimer. The constrained structure of PCP allows one to focus on the most important degree of freedom, the inter-ring distance. The calculations explain the main features of the transient absorption spectral evolution. This brightest transition of the excimer is polarized along the inter-fragment axis. The absorption of light polarized in the plane of the rings reveals the presence of other absorbing states of Rydberg character, with much weaker intensities. We also report new transient absorption data obtained by a broadband 8 fs pump, which time-resolve strong modulations of the excimer absorption. The combination of theory and experiment provides a detailed picture of the evolution of the electronic structure of the PCP excimer in the course of a single molecular vibration.

This study overviews and extends a recently developed stochastic finite-temperature Kohn-Sham density functional theory to study warm dense matter using Langevin dynamics, specifically under periodic boundary conditions. The method's algorithmic complexity exhibits nearly linear scaling with system size and is inversely proportional to the temperature. Additionally, a novel linear-scaling stochastic approach is introduced to assess the Kubo-Greenwood conductivity, demonstrating exceptional stability for DC conductivity. Utilizing the developed tools, we investigate the equation of state, radial distribution, and electronic conductivity of Hydrogen at a temperature of 30,000K. As for the radial distribution functions, we reveal a transition of Hydrogen from gas-like to liquid-like behavior as its density exceeds 4 g/cm³. As for the electronic conductivity as a function of the density, we identified a remarkable isosbestic point at frequencies around 7eV, which may be an additional signature of a gas-liquid transition in Hydrogen at 30,000K.

Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons quantum nature allows its transfer across long distances. In the well-known harpoon mechanism, electron-transfer results in Coulombic attraction between initially neutral reactants that leads to dramatic increase in the reaction rate. Here we present a different mechanism, in which electron-transfer from a neutral reactant to a multiply charged cation results in strong repulsion that encodes the electron-transfer distance in the kinetic energy release. 3D coincidence-imaging allows to identify such “inverse” harpoon products, predicted by non adiabatic molecular dynamics simulations to occur between H2 and HCOH2+ following double-ionization of isolated methanol molecules. Detailed comparison of measured and simulated data indicates that while the relative probability of long-range electron-transfer events is correctly predicted, theory overestimates the electron-transfer distance.

We develop a formalism for calculating forces on the nuclei within the linear-scaling stochastic density functional theory (sDFT) in a nonorthogonal atomcentered basis set representation (Fabian et al. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2019, 9, e1412, 10.1002/wcms.1412) and apply it to the Tryptophan Zipper 2 (Trpzip2) peptide solvated in water. We use an embedded-fragment approach to reduce the statistical errors (fluctuation and systematic bias), where the entire peptide is the main fragment and the remaining 425 water molecules are grouped into small fragments. We analyze the magnitude of the statistical errors in the forces and find that the systematic bias is of the order of 0.065 eV/Å (∼1.2 × 10−3Eh/a0) when 120 stochastic orbitals are used, independently of system size. This magnitude of bias is sufficiently small to ensure that the bond lengths estimated by stochastic DFT (within a Langevin molecular dynamics simulation) will deviate by less than 1% from those predicted by a deterministic calculation.

The trihydrogen ion has a central role in creating complex molecules in the interstellar medium. Therefore, its formation and destruction mechanisms in high photon energy environments involving organic molecules are drawing significant experimental and theoretical attention. Here, we employ a combination of time-resolved ultrafast extreme-ultraviolet pump and near-infrared probe spectroscopy applied to the deuterated CH3OD methanol molecule. Similar to other double-ionization studies, the isotopic labeling reveals two competing pathways for forming trihydrogen: A) H+3 + COH+ and B) H+3 + HCO+. We validate our high-level ab initio nonadiabatic molecular dynamic simulations by showing that it closely reproduces the essential features of the measured kinetic energy release distribution and branching ratios of the two pathways of the deuterated system. The success of ab initio simulation in describing single photon double-ionization allows for an unprecedented peek into the formation pathways for the undeuterated species, beyond present experimental reach. For this case, we find that the kinetic energy release of pathway B shifts to lower energies by more than 0.6 eV due to a dynamical isotope effect. We also determine the mechanism for trihydrogen formation from excited states of the dication and elucidate the isotope effect’s role in the observed dynamics.

Despite the abundance of data concerning single-photon double ionization of methanol, the spin state of the emitted electron pair has never been determined. Here we present the first evidence that identifies the emitted electron pair spin as overwhelmingly singlet when the dication forms in low-energy configurations. The experimental data show that while the yield of the CH2O+ + H3+ Coulomb explosion channel is abundant, the metastable methanol dication is largely absent. According to high-level ab initio simulations, these facts indicate that photoionization promptly forms singlet dication states, where they quickly decompose through various channels, with significant H3+ yields on the low-lying states. In contrast, if we assume that the initial dication is formed in one of the low-lying triplet states, the ab initio simulations exhibit a metastable dication, contradicting the experimental findings. Comparing the average simulated branching ratios with the experimental data suggests a \textgreater3 order of magnitude enhancement of the singlet:triplet ratio compared with their respective 1:3 multiplicities.

Efficient Boltzmann-sampling using first-principles methods is challenging for extended systems due to the steep scaling of electronic structure methods with the system size. Stochastic approaches provide a gentler system-size dependency at the cost of introducing "noisy" forces, which serve to limit the efficiency of the sampling. In the first-order Langevin dynamics (FOLD), efficient sampling is achievable by combining a well-chosen preconditioning matrix S with a time-step-bias-mitigating propagator (Mazzola et al., Phys. Rev. Lett., 118, 015703 (2017)). However, when forces are noisy, S is set equal to the force-covariance matrix, a procedure which severely limits the efficiency and the stability of the sampling. Here, we develop a new, general, optimal, and stable sampling approach for FOLD under noisy forces. We apply it for silicon nanocrystals treated with stochastic density functional theory and show efficiency improvements by an order-of-magnitude.

Abstract The Kubo-Greenwood (KG) formula is often used in conjunction with Kohn-Sham (KS) density functional theory (DFT) to compute the optical conductivity, particularly for warm dense mater. For applying the KG formula, all KS eigenstates and eigenvalues up to an energy cutoff are required and thus the approach becomes expensive, especially for high temperatures and large systems, scaling cubically with both system size and temperature. Here, we develop an approach to calculate the KS conductivity within the stochastic DFT (sDFT) framework, which requires knowledge only of the KS Hamiltonian but not its eigenstates and values. We show that the computational effort associated with the method scales linearly with system size and reduces in proportion to the temperature unlike the cubic increase with traditional deterministic approaches. In addition, we find that the method allows an accurate description of the entire spectrum, including the high-frequency range, unlike the deterministic method which is compelled to introduce a high-frequency cut-off due to memory and computational time constraints. We apply the method to helium-hydrogen mixtures in the warm dense matter regime at temperatures of \textbackslashsim60\textbackslashtext\kK\ and find that the system displays two conductivity phases, where a transition from non-metal to metal occurs when hydrogen atoms constitute \textbackslashsim0.3 of the total atoms in the system.

A multifaceted agreement between ab initio theoretical predictions and experimental measurements, including branching ratios, channel-specific kinetic energy release, and three-body momentum correlation spectra, leads to the identification of new mechanisms in Coulomb-explosion (CE) induced two- and three-body breakup processes in methanol. These identified mechanisms include direct nonadiabatic Coulomb explosion responsible for CO bond-breaking, a long-range “ inverse harpooning” dominating the production of H2+ + HCOH+, a transient proton migration leading to surprising energy partitioning in three-body fragmentation and other complex dynamics forming products such as H2O+ and H3+. These mechanisms provide general concepts that should be useful for analyzing future time-resolved Coulomb explosion imaging of methanol as well as other molecular systems. These advances are enabled by a combination of recently developed experimental and computational techniques, using weak ultrafast EUV pulses to initiate the CE and a high-level quantum chemistry approach to follow the resulting field-free nonadiabatic molecular dynamics.

Single-photon Coulomb explosion of methanol is instigated using the broad bandwidth pulse achieved through high-order harmonics generation. Using 3D coincidence fragment imaging of one molecule at a time, the kinetic energy release (KER) and angular distributions of the products are measured in different Coulomb explosion (CE) channels. Two-body CE channels breaking either the C–O or the C–H bonds are described as well as a proton migration channel forming H2O+, which is shown to exhibit higher KER. The results are compared to intense-field Coulomb explosion measurements in the literature. The interpretation of broad bandwidth single-photon CE data is discussed and supported by ab initio calculations of the predominant C–O bond breaking CE channel. We discuss the importance of these findings for achieving time resolved imaging of ultrafast dynamics.

An ab initio Langevin dynamics approach is developed based on stochastic density functional theory (sDFT) within a new embedded fragment formalism. The forces on the nuclei generated by sDFT contain a random component natural to Langevin dynamics and its standard deviation is used to estimate the friction term on each atom by satisfying the fluctuation–dissipation relation. The overall approach scales linearly with system size even if the density matrix is not local and is thus applicable to ordered as well as disordered extended systems. We implement the approach for a series of silicon nanocrystals (NCs) of varying size with a diameter of up to 3nm corresponding to Ne = 3000 electrons and generate a set of configurations that are distributed canonically at a fixed temperature, ranging from cryogenic to room temperature. We also analyze the structure properties of the NCs and discuss the reconstruction of the surface geometry.

We study the photodissociation of the H+2 molecule by ultrashort Fock-state electromagnetic pulses (EMPs). We use the Born-Oppenheimer treatment combined with an explicit photon number representation via diabatic electrophoton potential surfaces for simplification of the basic equations. We discuss the issue of the number of photon states required and show that six photon states enable good accuracy for photoproduct kinetic energies of up to 3 eV. We calculate photodissociation probabilities and nuclear kinetic-energy (KE) distributions of the photodissociation products for 800 nm, 50-TW/cm2 pulses. We show that KE distributions depend on three pulse durations of 10, 20, and 45 fs and on various initial vibrational states of the molecule. We compare the Fock-state results to those obtained by “conventional,” i.e., coherent-state, laser pulses of equivalent electric fields and durations. The effects of the quantum state of EMPs on the photodissociation dynamics are especially strong for high initial vibrational states of H+2. While coherent-state pulses suppress photodissociation for the high initial vibrational states of H+2, the Fock-state pulses enhance it.

Producing and controlling nonclassical light states are now the subject of intense experimental efforts. In this paper we consider the interaction of such a light state with a small molecule. Specifically, we develop the theory and apply it numerically to calculate in detail how a short pulse of nonclassical light, such as the high intensity Fock state, induces photodissociation in H2+. We compare the kinetic energy distributions and photodissociation yields with the analogous results of quasi-classical light, namely a coherent state. We find that Fock-state light decreases the overall probability of dissociation for low vibrational states of H2+ as well as the location of peaks and line shapes in the kinetic energy distribution of the nuclei.

Pinpointing extrema on a multidimensional hypersurface is an important generic problem with a broad scope of application in statistical mechanics, biophysics, chemical reaction dynamics, and quantum chemistry. Local minima of the hypersurface correspond to metastable structures and are usually the most important points to look for. They are relatively easy to find using standard minimizing algorithms. A considerably more difficult task is the location of saddle points. The saddle points most sought for are those which form the lowest barriers between given minima and are usually required for determining rates of rare events. We formulate a path functional minimum principle for the saddle point. We then develop a cubic spline method for applying this principle and locating the saddle point(s) separating two local minima on a potential hypersurface. A quasi-Newton algorithm is used for minimization. The algorithm does not involve second derivatives of the hypersurface and the number of potential gradients evaluated is usually less than 10% of the number of potential evaluations. We demonstrate the performance of the method on several standard examples and on a concerted exchange mechanism for self-diffusion in diamond. Finally, we show that the method may be used for solving large constrained minimization problems which are relevant for self-consistent field iterations in large systems.

The presence of helium in carbon systems, such as diamonds and fullerenes is of interest for planetary sciences, geophysics, astrophysics, and evolution biology. Such systems typically involve a large number of atoms and require a fast method for assessing the interaction potential and forces. We developed a tight-binding approach, based on density functional calculations, which includes a many-body potential term. This latter term is essential for consolidating the density functional results of helium in bulky diamond and Helium passing through a benzene ring which is important for helium-fullerene applications. The method is simple to apply and exhibits good transferability properties.

Real-time first principle simulations are presented of the D2 Coulomb explosion dynamics detonated by exposure to very intense few-cycle laser pulse. Three approximate functionals within the time-dependent density functional theory (TDDFT) functionals are examined for describing the electron dynamics, including time-dependent Hartree-Fock theory. Nuclei are treated classically with quantum corrections. The calculated results are sensitive to the underlying electronic structure theory, showing too narrow kinetic energy distribution peaked at too high kinetic energy when compared with recent experimental results (Phys. Rev. Lett. 2003, 91, 093002). Experiment also shows a low energy peak which is not seen in the present calculation. We conclude that while Ehrenfest-adiabatic-TDDFT can qualitatively account for the dynamics, it requires further development, probably beyond the adiabatic approximation, to be quantitative.

Dynamics of glycine chemisorbed on the surface of a silicon cluster is studied for a process that involves single-photon ionization, followed by recombination with the electron after a selected time delay. The process is studied by “on-the-fly” molecular dynamics simulations, using the semiempirical parametric method number 3 (PM3) potential energy surface. The system is taken to be in the ground state prior to photoionization, and time delays from 5 to 50 fs before the recombination are considered. The time evolution is computed over 10 ps. The main findings are (1) the positive charge after ionization is initially mostly distributed on the silicon cluster. (2) After ionization the major structural changes are on the silicon cluster. These include Si–Si bond breaking and formation and hydrogen transfer between different silicon atoms. (3) The transient ionization event gives rise to dynamical behavior that depends sensitively on the ion state lifetime. Subsequent to 45 fs evolution in the charged state, the glycine molecule starts to rotate on the silicon cluster. Implications of the results to various processes that are induced by transient transition to a charged state are discussed. These include inelastic tunneling in molecular devices, photochemistry on conducting surfaces, and electron-molecule scattering.