Multipathway dissociation dynamics of core-excited methyl chloride probed by high resolution electron spectroscopy and Auger-electron-ion coincidences

Core excitation triggers nuclear dynamics on the femtosecond time scale. A multiparametric electron/ion coincidence approach has been used to disentangle complex decay processes occurring at short (molecular) or long (atomic) time scales. Methyl chloride has been excited by scanning along the dissociative Cl2p-->sigma* resonance. The detailed chronology of the competing decay processes, leading to either the rearrangement product HCl(+), or an ultrafast dissociation leading to Cl(+), has been investigated. The observed Auger-Doppler shift has been analyzed for various orientations of the electron and fragment ion.     

Induced currents and electron counting in aromatic boron wheels: B8(2-) and B9-)

The newly discovered atom-centered polygonal wheels B8(2-) and B9- are predicted to show ring currents characteristic of aromatic systems. Ipsocentric mapping of induced current density for both molecules attributes a pi diatropic current to the four electrons of the doubly degenerate pi HOMO and a sigma diatropic current to the four electrons of the doubly degenerate sigma HOMO, each orbital pair having an available transition to corresponding LUMO orbitals in which the angular node count increases by one. Thus, on the magnetic criterion, B8(2-) and B9- are each both pi- and sigma-aromatic as a consequence of the nodal properties of the frontier orbitals of the pi- and sigma-stacks.     

Ring-current models from the differential Biot-Savart law

The differential Biot-Savart law provides simple models for the pi ring currents induced in diatropic and paratropic planar conjugated molecules by a perpendicular magnetic field. The model predictions are confirmed by ab initio maps of nuclear magnetic shielding density. The effects on the protons and on the ring carbon atoms from the closest and furthest segments of the current loop are easily interpreted. [structure: see text]     

The aromatic character of magnesium porphyrins

The aromaticity of magnesium porphyrins have been studied by calculating the nuclear magnetic shieldings in selected points outside the molecules. The strength of the induced ring currents for a given magnetic field have been obtained by using the aromatic-ring-current-shielding (ARCS) method. Nucleus-independent chemical shift (NICS) calculations provide additional information about the current routes in the multiple-ring systems. The total aromatic pathway of magnesium porphyrins must be considered as a superposition of several (4n + 2) pi-electron Huckel pathways. We found that all beta-unsaturated pyrrolic rings have local ring currents the strength of which is 70-90% of the current strength for the pyrrole molecule. The present study also shows that the 18pi-[16]annulene aromatic pathway does not exist in magnesium porphyrins until all four pyrrolic units are saturated in the beta-position.     

Aromaticity of N-heterocyclic carbene and its analogues: Magnetically induced ring current perspective

The N-heterocyclic carbene, imidazole-2-ylidene, and its main group (13-15) analogues contain cyclically conjugated 6π electrons. Experimental ¹H nuclear magnetic resonance (NMR) spectra suggest an increase in aromaticity along a period from left to right. Whereas the order along a group is as follows: period 2 > period 5 > period 4 > period 3 due to change in structure. To understand the order of aromaticity, the magnetically induced ring currents of the molecules are calculated using aromatic ring current shielding, gauge-including magnetically induced currents (GIMIC) method and Stanger's σ-model applying the gauge-including atomic orbitals NMR technique. It is found that GIMIC best describes the order of aromaticity especially along a group where current-profile changes on the bivalent atom down a group due to change in electron density. Moreover, the GIMIC provides the visualization of current by sign modulus and the anisotropy of the induced current density plots.     

The NICS‐XY‐Scan: Identification of Local and Global Ring Currents in Multi‐Ring Systems

Nucleus‐independent chemical shift (NICS)‐based methods are very popular for the determination of the induced magnetic field under an external magnetic field. These methods are used mostly (but not only) for the determination of the aromaticity and antiaromaticity of molecules and ions, both qualitatively and quantitatively. The ghost atom that serves as the NICS probe senses the induced magnetic field and reports it in the form of an NMR chemical shift. However, the source of the field cannot be determined by NICS. Thus, in a multi‐ring system that may contain more than one induced current circuit (and therefore more than one source of the induced magnetic field) the NICS value may represent the sum of many induced magnetic fields. This may lead to wrong assignments of the aromaticity (and antiaromaticity) of the systems under study. In this paper, we present a NICS‐based method for the determination of local and global ring currents in conjugated multi‐ring systems. The method involves placing the NICS probes along the X axis, and if needed, along the Y axis, at a constant height above the system under study. Following the change in the induced field along these axes allows the identification of global and local induced currents. The best NICS type to use for these scans is NICS_πZZ, but it is shown that at a height of 1.7 Å above the molecular plane, NICS_ZZ provides the same qualitative picture. This method, namely the NICS‐XY‐scan, gives information equivalent to that obtained through current density analysis methods, and in some cases, provides even more details.     

Counter‐Rotating Spin‐Polarised Ring Currents in Odd‐Electron Carbocycles

We propose a molecular‐orbital model to explain how majority and minority spins in odd‐π‐electron carbocycles sustain counter‐rotating magnetic‐field‐induced ring currents. The model is based on the ipsocentric approach to magnetic response, in which ring currents are dominated by frontier‐orbital contributions obeying angular‐momentum selection rules. Coupled unrestricted Hartree–Fock ab initio calculations of the ring‐current responses for singly charged benzene and planarised cyclo‐octatetraene ions confirm the predictions of the qualitative model, and are consistent with correlated MP2 spin‐polarised current calculations.     

Electronic spectroscopy and ultrafast energy relaxation pathways in the lowest Rydberg States of trimethylamine

Resonance-enhanced multiphoton ionization photoelectron spectroscopy has been applied to study the electronic spectroscopy and relaxation pathways among the 3p and 3s Rydberg states of trimethylamine. The experiments used femtosecond and picosecond duration laser pulses at wavelengths of 416, 266, and 208 nm and employed two-photon and three-photon ionization schemes. The binding energy of the 3s Rydberg state was found to be 3.087 +/- 0.005 eV. The degenerate 3p x, y states have binding energies of 2.251 +/- 0.005 eV, and 3p z is at 2.204 +/- 0.005 eV. Using picosecond and femtosecond time-resolved experiments we spectrally and temporally resolved an intricate sequence of energy relaxation pathways leading from the 3p states to the 3s state. With excitation at 5.96 eV, trimethylamine is found to decay from the 3p z state to 3p x, y in 539 fs. The decay to 3s from all the 3p states takes place with a 2.9 ps time constant. On these time scales, trimethylamine does not fragment at the given internal energies, which range from 0.42 to 1.54 eV depending on the excitation wavelength and electronic state.     

A dissected ring current model for assessing magnetic aromaticity: a general approach for both organic and inorganic rings

A model based on classical electrodynamics is used to measure the strength of ring currents of different molecular orbitals, i.e., σ- and π-orbitals, and characteristics of ring current loops, i.e., ring current radii and height of current loops above/below the ring planes, among a number of organic as well as inorganic molecules. For the π-current, the present model represents an improvement of previous approaches to determine ring current intensity. It is proven that the present model is more precise than previous models as they could not explain presence of the minimum in the plot of NICS(πzz) versus distance close to the ring plane. Variations in the charge of molecules and the types of constituent atoms of each species affect the ring current radii of both σ- and π-current loops as well as the height of π-current loops above/below the ring plane. It is suggested that variation in the distribution of the one-electron density in different systems is the main source of differences of the ring current characteristics.     

Beyond NICS: estimation of the magnetotropicity of inorganic unsaturated planar rings

A simple classical model of magnetic-field induced electron flow is used to evaluate the ring current strength for a few inorganic monocyclic compounds: B(3)H(3)N(3), B(3)H(3)O(3), P(6), N(6), Si(6)H(6), N, Al and H(6). It is shown that, for these neutral and charged systems, sustaining delocalized electron currents in the presence of a magnetic field B(ext) orthogonal to the σ(h) plane, the out-of-plane component of the nuclear magnetic shielding along the central axis is connected to the out-of-plane magnetizability by a simple equation, involving the radius of an average loop of current. A novel estimate of this effective radius is provided. Reliable ring current susceptibilities (that is, current strengths) can be evaluated by a simple relationship, using the out-of-plane components of nuclear shielding and magnetizability tensors. The accuracy of the current susceptibilities calculated by the classical model is established by comparison with corresponding ab initio estimates obtained by integrating the quantum mechanical current-density vector field. The out-of-plane components of nuclear shielding and magnetizability are both strongly biased by the molecular geometry. Their combined use to estimate the ring current susceptibility offers a quantifier of magnetotropicity more reliable than (i) the ξ(∥) out-of-plane component of magnetizability, (ii) the σ(∥)(CM) out-of-plane component of the magnetic shielding at the center of mass, widely reported as NICS(∥)(0) = -σ(∥)(CM). The inadequacy of these commonly adopted magnetotropicity measures is demonstrated by comparing a set of related molecules, C(6)H(6) and Si(6)H(6), N(6) and P(6).     

Generating long-lasting 1H and 13C hyperpolarization in small molecules with parahydrogen-induced polarization

Recently, Levitt and co-workers demonstrated that conserving the population of long-lasting nuclear singlet states in weak magnetic fields can lead to a preservation of nuclear spin information over times substantially longer than governed by the (high-field) spin-lattice relaxation time T1. Potential benefits of the prolonged spin information for magnetic resonance imaging and spectroscopy were pointed out, particularly when combined with the parahydrogen induced polarization (PHIP) methodology. In this contribution, we demonstrate that an increase of the effective relaxation time by a factor up to three is achieved experimentally, when molecules hyperpolarized by PHIP are kept in a weak magnetic field instead of the strong field of a typical NMR magnet. This increased lifetime of spin information makes the known PHIP phenomena more compatible with the time scales of biological processes and, thus, more attractive for future investigations.     

Femtosecond dynamics of Cu(CD3OD)

We report the femtosecond nuclear dynamics of Cu(CD3OD) van der Waals clusters, investigated using photodetachment-photoionization spectroscopy. Photodetachment of an electron from Cu-(CD3OD) with a 150 fs, 398 nm laser pulse produces a vibrationally excited neutral complex that undergoes ligand reorientation and dissociation. The dynamics of Cu(CD3OD) on the neutral surface is interrogated by delayed femtosecond resonant two-photon ionization. Analysis of the resulting time-dependent signals indicates that the nascent Cu(CD3OD) complex dissociates on two distinct time scales of 3 and 30 ps. To understand the origins of the observed time scales, complimentary studies were performed. These included measurement of the photoelectron spectrum of Cu-(CD3OD) as well as a series of calculations of the structure and the electronic and vibrational energies of the anion and neutral complexes. Based on the comparisons of the experimental and calculated results for Cu(CD3OD) with those obtained from earlier studies of Cu(H2O), we conclude that the 3 ps time scale reflects the energy transfer from the rotation of CD3OD in the complex to the dissociation coordinate, while the 30 ps time scale reflects the energy transfer from the excited methyl torsion states to the dissociation coordinate.     

Self-diffusion in two-dimensional hard ellipsoid suspensions

We studied the self-diffusion of colloidal ellipsoids in a monolayer near a flat wall by video microscopy. The image processing algorithm can track the positions and orientations of ellipsoids with subpixel resolution. The translational and rotational diffusions were measured in both the laboratory frame and the body frame along the long and short axes. The long-time and short-time diffusion coefficients of translational and rotational motions were measured as functions of the particle concentration. We observed the nondiffusive crossover region in the intermediate time regime due to the caging of neighboring particles. Both the beginning and the ending times of the intermediate regime exhibit power-law dependence on concentration. The long-time and short-time diffusion anisotropies change nonmonotonically with concentration and reach minima in the semidilute regime because the motions along long axes are caged at lower concentrations than the motions along short axes. The time derivatives of mean-square displacements change linearly with the inverse of time in the intermediate time regimes at various particle densities. This indicates that their relaxation functions decay as 1/t which provides new challenges in theory. The effects of coupling between rotational and translational Brownian motions were demonstrated and the two time scales corresponding to anisotropic particle shape and anisotropic neighboring environment were measured.     

Diffusion damping during adiabatic z-rotation pulses for NMR spectroscopy in inhomogeneous magnetic fields

High-resolution nuclear magnetic resonance spectra from samples located in inhomogeneous static and radio frequency magnetic fields can be obtained by applying a train of z-rotation radio frequency pulses to repeatedly refocus the inhomogeneous broadening during signal detection. z-rotation pulses based on an adiabatic double passage are effective over wide bandwidths using a limited amount of radio frequency power at the expense of being time consuming and, consequently, sensitive to motion of the spin bearing molecules. The signal damping resulting from molecular self-diffusion during the pulse was studied experimentally and using Brownian dynamics simulations. The results show that the analytical expression for diffusion damping during a double spin echo is a reasonable approximation for the signal decay during an adiabatic z-rotation pulse. Methods to alleviate the effects of diffusion are discussed.     

Magnetic fields in electrochemistry: The Lorentz force. A mini-review

Some recent work on the flow induced by uniform or non-uniform magnetic fields acting on currents in an electrochemical cell is reviewed. The effects include modifying the structure and texture of electrodeposits including their chirality, controlling hydrogen bubble release, inducing microfluidic flow and influencing nucleation. Much of this depends on micro-magnetohydrodynamic flow, on a scale of microns.     

Spatial ring current model for the prismane molecule

Spatial models of magnetic-field induced electronic ring currents have been constructed for the prismane molecule via stagnation graphs and current density maps. These tools provide an insight into the complicated phenomenology resulting from competition of diatropic and paratropic regimes that determine the magnitude of various components of magnetic susceptibility and magnetic shielding of hydrogen and carbon nuclei. Shielding density maps show that the differential Biot-Savart law, along with an atlas of the current density field, explains magnetic shielding at hydrogen and carbon nuclei and virtual shielding at ring and cage centers.     

Diatropicity of tetraazanaphthalenes

Tetraazanaphthalenes are diatropic molecules, whose magnetic response to a magnetic field perpendicular to the molecular plane closely resembles that of naphthalene. The out-of-plane component of the magnetic susceptibility tensor and its strong anisotropy can be used as quantifiers of magnetic aromaticity. Maps showing streamlines and modulus of the current density field provide clear evidence for diatropicity of these systems. They also explain the strong anisotropy of carbon and nitrogen magnetic shielding, which is determined by the big out-of-plane component of the nuclear shielding tensor. The electronic ring currents observed in the map deshield the nuclei of ring hydrogens by enforcing the local magnetic field and diminishing the out-of-plane component of proton shielding.     

Ultrafast photofragmentation dynamics of molecular iodine driven with timed XUV and near-infrared light pulses

Photofragmentation dynamics of molecular iodine was studied as a response to the joint illumination with femtosecond 800 nm near-infrared and 13 nm extreme ultraviolet (XUV) pulses delivered by the free-electron laser facility FLASH. The interaction of the molecular target with two light pulses of different wavelengths but comparable pulse energy elucidates a complex intertwined electronic and nuclear dynamics. To follow distinct pathways out of a multitude of reaction channels, the recoil of created ionic fragments is analyzed. The delayed XUV pulse provides a way of following molecular photodissociation of I(2) with a characteristic time-constant of (55 ± 10) fs after the laser-induced formation of antibonding states. A preceding XUV pulse, on the other hand, preferably creates a 4d(-1) inner-shell vacancy followed by the fast Auger cascade with a revealed characteristic time constant τ(A2)=(23±11) fs for the second Auger decay transition. Some fraction of molecular cationic states undergoes subsequent Coulomb explosion, and the evolution of the launched molecular wave packet on the repulsive Coulomb potential was accessed by the laser-induced postionization. A further unexpected photofragmentation channel, which relies on the collective action of XUV and laser fields, is attributed to a laser-promoted charge transfer transition in the exploding molecule.     

Vibrational dynamics of deoxyguanosine 5'-monophosphate following UV excitation

The relaxation dynamics of the DNA nucleotide deoxyguanosine 5'-monophosphate (dGMP) following 266 nm photoexcitation has been studied by transient IR spectroscopy with femtosecond time resolution. The induced dynamics of the amide I (carbonyl) stretch, the asymmetric guanine ring stretch and the phosphate asymmetric stretch are monitored in the region 1000-1800 cm(-1). Excitation and subsequent rapid internal conversion to a "hot" ground state is reflected by depletion of the vibrational ground states of the amide I stretch and guanine ring stretch. However, the vibrational ground state of the phosphate is left unperturbed, indicating the absence of vibrational coupling between the guanine ring system and the phosphate group. The vibrational ground state of the amide I is repopulated in 2.5 ps (±0.2 ps) while it takes 3.7 ps (±0.5 ps) to repopulate the guanine ring vibration. This article discusses two possible relaxation pathways of dGMP, as well as the implications of the weak phosphate dynamics.