On the rate constant for reactions between ions in solution: a simple unification of the Born and Debye-Hückel models.

The rate of reaction between ions in solution depends on solvent properties like permittivity and ionic strength. The influence of a solution's ionic strength is described by the Brønsted-Bjerrum equation. We show how this equation can be derived directly from transition-state theory without introducing the concept of activity coefficients.

Dissociation of HeH in the electronic ground state using shaped mid-IR laser pulses.

Inspired by recent experimental work, we study the control over the laser-driven dissociation of the HeH ion in the electronic ground state. Shaped pulses with peak intensities below 10 W cm are obtained by phase modulation of high-intensity transform-limited femtosecond pulses. We investigate the performance of pulse shaping for a number of shaping parameters targeting both vibrational and rotational excitation pathways.

Quantum control of field-free molecular orientation.

Generating field-free (non-stationary) orientation of molecules in space has been a longstanding goal in the field of quantum control of molecular rotation, which has significant applications in physical chemistry, chemical physics, strong-field physics, and quantum information science. In this Perspective, we review and examine several representative control schemes developed in recent years and implemented in theoretical and experimental areas for generating field-free orientation of molecules. By conducting numerical simulations of different control schemes on the same molecular system, we demonstrate that quantum coherent control, specifically targeting a limited number of the lowest-lying rotational levels to achieve an optimal superposition, can result in a high degree of orientation.

Quantum Coherent Control of a Single Molecular-Polariton Rotation.

We present a combined analytical and numerical study for coherent terahertz control of a single molecular polariton, formed by strongly coupling two rotational states of a molecule with a single-mode cavity. Compared to the bare molecules driven by a single terahertz pulse, the presence of a cavity strongly modifies the postpulse orientation of the polariton, making it difficult to obtain its maximal degree of orientation. To solve this challenging problem toward achieving complete quantum coherent control, we derive an analytical solution of a pulse-driven quantum Jaynes-Cummings model by expanding the wave function into entangled states and constructing an effective Hamiltonian.

Tracking structural solvent reorganization and recombination dynamics following e photoabstraction from aqueous I with femtosecond x-ray spectroscopy and scattering.

We present a sub-picosecond resolved investigation of the structural solvent reorganization and geminate recombination dynamics following 400 nm two-photon excitation and photodetachment of a valence p electron from the aqueous atomic solute, I(aq). The measurements utilized time-resolved X-ray Absorption Near Edge Structure (TR-XANES) spectroscopy and X-ray Solution Scattering (TR-XSS) at the Linac Coherent Light Source x-ray free electron laser in a laser pump/x-ray probe experiment. The XANES measurements around the L-edge of the generated nascent iodine atoms (I) yield an average electron ejection distance from the iodine parent of 7.

Femtochemistry of bimolecular reactions from weakly bound complexes: computational study of the H + H'OD → H'OH + D or HOD + H' exchange reactions.

A full-dimensional wavepacket propagation describing the bimolecular exchange reactions H + H'OD → H'OH + D or HOD + H' initiated by photolysis of HCl in the hydrogen-bound complex (HCl)⋯(HOD) is reported. The dynamics of this reaction is carried out with the MCTDH method on an potential energy surface (PES) of HO and the initial state is derived from the ground state wavefunction of the complex obtained by relaxation on its own electronic ground state PES. The description of the system makes use of polyspherical coordinates parametrizing a set of Radau and Jacobi vectors.

On Weak-Field (One-Photon) Coherent Control of Photoisomerization.

Photochemistry induced by phase-coherent laser light is an intriguing topic. The possibility of weak-field (one-photon) phase-only control of photoisomerization is controversial. Experimental studies on the weak-field coherent control of cis-trans isomerization have led to conflicting results.

Mechanism of Photoinduced Dihydroazulene Ring-Opening Reaction.

The photoinduced ring-opening reaction is a key process in the functioning of dihydroazulene/vinylheptafulvene (DHA/VHF) photoswitches. Over the years, the mechanism of this reaction has been extensively debated. Herein, by means of nonadiabatic trajectory dynamics simulations and quantum chemistry calculations, we present the first detailed and comprehensive investigation on the mechanism of the photoinduced ring-opening reaction of DHA.

Electronic Coherence in Ultrafast X-Ray Scattering from Molecular Wave Packets.

Simulations of nonresonant ultrafast x-ray scattering from a molecular wave packet in H_{2} are used to examine and classify the components that contribute to the total scattering signal. The elastic component, which can be used to determine the structural dynamics of the molecule, is also found to carry a strong signature of an adiabatic electron transfer that occurs in the simulated molecule. The inelastic component, frequently assumed to be constant, is found to change with the geometry of the molecule.

Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule.

We report x-ray free electron laser experiments addressing ground-state structural dynamics of the diplatinum anion Pt_{2}POP_{4} following photoexcitation. The structural dynamics are tracked with <100  fs time resolution by x-ray scattering, utilizing the anisotropic component to suppress contributions from the bulk solvent. The x-ray data exhibit a strong oscillatory component with period 0.

Excited-state solvation structure of transition metal complexes from molecular dynamics simulations and assessment of partial atomic charge methods.

In this work, we investigate the excited-state solute and solvation structure of [Ru(bpy)3]2+, [Fe(bpy)3]2+, [Fe(bmip)2]2+ and [Cu(phen)2]+ (bpy = 2,2'-bipyridine; bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine; phen = 1,10-phenanthroline) transition metal complexes (TMCs) in terms of solute-solvent radial distribution functions (RDFs) and evaluate the performance of some of the most popular partial atomic charge (PAC) methods for obtaining these RDFs by molecular dynamics (MD) simulations. To this end, we compare classical MD of a frozen solute in water and acetonitrile (ACN) with quantum mechanics/molecular mechanics Born-Oppenheimer molecular dynamics (QM/MM BOMD) simulations. The calculated RDFs show that the choice of a suitable PAC method is dependent on the coordination number of the metal, denticity of the ligands, and type of solvent.

Breaking dynamic inversion symmetry in a racemic mixture using simple trains of laser pulses.

Recent advances in ultrafast laser technology hint at the possibility of using shaped pulses to generate deracemization via selective enantiomeric conversion; however, experimental implementation remains a challenge and has not yet been achieved. Here, we describe an experiment that can be considered an accessible intermediate step on the road towards achieving laser induced deracemization in a laboratory. Our approach consists of driving a racemic mixture of 3D oriented 3,5-difluoro-3', 5'-dibromobiphenyl (FHC-CHBr) molecules with a simple train of Gaussian pulses with alternating polarization axes.

Electronic structure and rovibrational predissociation of the 2Π state in KLi.

Adiabatic potential energy curves of the 31Σ+, 33Σ+, 21Π and 23Π states correlating for large internuclear distance with the K(4s) + Li(2p) atomic asymptote were calculated. Very good agreement between the calculated and the experimental curve of the 21Π state allowed for a reliable description of the dissociation process through a small (∼20 cm-1 for J = 0) potential energy barrier. The barrier supports several rovibrational quasi-bound states and explicit time evolution of these states via the time-dependent nuclear Schrödinger equation, showed that the state populations decay exponentially in time.

Non-resonant vibrational excitation of HOD and selective bond breaking.

This paper reports a time-dependent quantum mechanical wave packet study for bond-selective excitation and dissociation of HOD into the H + OD and D + OH channels in the first absorption band. Prior to excitation, the HOD molecule is randomly oriented with respect to a linearly polarized laser field and accurate static dipole moment and polarizability surfaces are included in the interaction potential. Vibrational excitation is obtained with intense, non-resonant 800 nm few-cycle excitation using dynamic Stark effect/impulsive Raman scattering.

Hyperfine-Structure-Induced Depolarization of Impulsively Aligned I_{2} Molecules.

A moderately intense 450 fs laser pulse is used to create rotational wave packets in gas phase I_{2} molecules. The ensuing time-dependent alignment, measured by Coulomb explosion imaging with a delayed probe pulse, exhibits the characteristic revival structures expected for rotational wave packets but also a complex nonperiodic substructure and decreasing mean alignment not observed before. A quantum mechanical model attributes the phenomena to coupling between the rotational angular momenta and the nuclear spins through the electric quadrupole interaction.

Anisotropy enhanced X-ray scattering from solvated transition metal complexes.

Time-resolved X-ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X-ray free-electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV-Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X-ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time-resolved X-ray scattering experiment.

Grid-Based Projector Augmented Wave (GPAW) Implementation of Quantum Mechanics/Molecular Mechanics (QM/MM) Electrostatic Embedding and Application to a Solvated Diplatinum Complex.

A multiscale density functional theory-quantum mechanics/molecular mechanics (DFT-QM/MM) scheme is presented, based on an efficient electrostatic coupling between the electronic density obtained from a grid-based projector augmented wave (GPAW) implementation of density functional theory and a classical potential energy function. The scheme is implemented in a general fashion and can be used with various choices for the descriptions of the QM or MM regions. Tests on HO clusters, ranging from dimer to decamer show that no systematic energy errors are introduced by the coupling that exceeds the differences in the QM and MM descriptions.

Electronic structure and time-dependent description of rotational predissociation of LiH.

The adiabatic potential energy curves of the Σ and Π states of the LiH molecule were calculated. They correlate asymptotically to atomic states, such as 2s + 1s, 2p + 1s, 3s + 1s, 3p + 1s, 3d + 1s, 4s + 1s, 4p + 1s and 4d + 1s. A very good agreement was found between our calculated spectroscopic parameters and the experimental ones.

Time-resolved X-ray scattering by electronic wave packets: analytic solutions to the hydrogen atom.

Modern pulsed X-ray sources permit time-dependent measurements of dynamical changes in atoms and molecules via non-resonant scattering. The planning, analysis, and interpretation of such experiments, however, require a firm and elaborated theoretical framework. This paper provides a detailed description of time-resolved X-ray scattering by non-stationary electronic wave packets in atomic systems.

Phase-Modulated Nonresonant Laser Pulses Can Selectively Convert Enantiomers in a Racemic Mixture.

Deracemization occurs when a racemic molecular mixture is transformed into a mixture containing an excess of a single enantiomer. Recent advances in ultrafast laser technology hint at the possibility of using shaped pulses to generate deracemization via selective enantiomeric conversion; however, experimental implementation remains a challenge and has not yet been achieved. Here we suggest a simple, yet novel approach to laser-induced enantiomeric conversion based on dynamic Stark control.

Atomistic characterization of the active-site solvation dynamics of a model photocatalyst.

The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir(dimen)], where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics.

Non-resonant dynamic stark control of vibrational motion with optimized laser pulses.

The term dynamic Stark control (DSC) has been used to describe methods of quantum control related to the dynamic Stark effect, i.e., a time-dependent distortion of energy levels.

Unravelling the role of quantum interference in the weak-field laser phase modulation control of photofragment distributions.

The role played by quantum interference in the laser phase modulation coherent control of photofragment distributions in the weak-field regime is investigated in detail in this work. The specific application involves realistic wave packet calculations of the transient vibrational populations of the Br2(B,vf) fragment produced upon predissociation of the Ne-Br2(B) complex, which is excited to a superposition of overlapping resonance states using different fixed bandwidth pulses where the linear chirps are varied. The postpulse transient phase modulation effects observed on fragment populations for a long time window are explained in terms of the mechanism of interference between overlapping resonances.