Quadrupole-bound Anion Research Articles

On the performance of second-order approximate coupled-cluster singles and doubles methods for non-valence anions.

We investigate the capability of several variants of the second-order approximate coupled-cluster singles and doubles (CC2) method to describe dipole-bound, quadrupole-bound, and correlation-bound molecular anions. The binding energy of anions formed by electron attachment to closed-shell molecules is computed using the electron attachment variant of CC2 (EA-CC2), whereas anions with a closed-shell ground state are treated with the standard CC2 method that preserves the number of particles. We find that EA-CC2 captures the binding energies of dipole-bound radical anions quite well, whereas results for other types of non-valence anions are less reliable. We also test the performance of semi-empirical spin-scaling factors for all types of non-valence anions and observe that the spin-scaled CC2 variants generally do not provide more accurate binding energies for dipole-bound anions, while the binding energies of quadrupole-bound and correlation-bound anions are improved. As exemplary applications of EA-CC2, we investigate the dipole-bound anions of the steroids cortisol, progesterone, and testosterone. In addition, we characterize electron attachment to sym-tetracyanonaphthalene, a molecule that supports five anionic states, two of which can be interpreted as hitherto unobserved π-type quadrupole-bound states.

The ground state, quadrupole-bound anion of succinonitrile revisited.

Using a combination of Rydberg electron transfer and negative ion photoelectron spectroscopy, we revisited an earlier study which, based on several separate pieces of evidence, had concluded that trans- and gauche-succinonitrile can form quadrupole bound anions (QBAs) and dipole bound anions (DBAs), respectively. In the present work, succinonitrile anions were formed by Rydberg electron transfer and interrogated by negative ion photoelectron spectroscopy. The resulting anion photoelectron spectra exhibited distinctive spectral features for both QBA and DBA species in the same spectrum, thereby providing direct spectroscopic confirmation of previous indirect conclusions. Just as importantly, this work also introduces the integrated combination of Rydberg electron transfer and anion photoelectron spectroscopy as a powerful, tandem technique for studying diffuse excess electron states.

Direct evidence for the ground state, quadrupole-bound anion of succinonitrile

A new article revisits previous work on succinonitrile anions in order to present more direct evidence for the existence of the quadrupole-bound anion state.

Electric dipole and quadrupole contributions to valence electron binding in a charge-screening environment

We make a multipole expansion of the atomic/molecular electrostatic charge distribution as seen by the valence electron up to the quadrupole term. The Tridiagonal Representation Approach (TRA) is used to obtain an exact bound state solution associated with an effective quadrupole moment and assuming that the electron-molecule interaction is screened by suborbital electrons. We show that the number of states available for binding the electron is finite forcing an energy jump in its transition to the continuum that could be detected experimentally in some favorable settings. We expect that our solution gives an alternative, viable and simple description of the binding of valence electron(s) in atoms/molecules with electric dipole and quadrupole moments. We also ascertain that our model implies that a pure quadrupole-bound anion cannot exist in such a charge-screening environment.

Observation of the dipole- and quadrupole-bound anions of 1,4-dicyanocyclohexane

Quadrupole-bound anions are negative ions in which their excess electrons are loosely bound by long-range electron-quadrupole attractions. Experimental evidence for quadrupole-bound anions has been scarce; until now, only trans-succinonitrile had been experimentally confirmed to form a quadrupole-bound anion. In this study, we present experimental evidence for a new quadrupole-bound anion. Our combined Rydberg electron transfer/anion photoelectron spectroscopy study demonstrates that the ee conformer of 1,4-dicyanocyclohexane (DCCH) supports a quadrupole-bound anion state, and that the cis-DCCH conformer forms a dipole-bound anion state. The electron binding energies of the quadrupole- and dipole-bound anions are measured as 18 and 115 meV, respectively, both of which are in excellent agreement with theoretical calculations by Sommerfeld.

Resonant spectra of quadrupolar anions

In quadrupole-bound anions, an extra electron is attached at a sufficiently large quadrupole moment of a neutral molecule, which is lacking a permanent dipole moment. The nature of the bound states and low-lying resonances of such anions is of interest for understanding the threshold behavior of open quantum systems in general. In this work, we investigate the properties of quadrupolar anions as halo systems, the formation of rotational bands, and the transition from a subcritical to supercritical electric quadrupole moment. We solve the electron-plus-rotor problem using a nonadiabatic coupled-channel formalism by employing the Berggren ensemble, which explicitly contains bound states, narrow resonances, and the scattering continuum. The rotor is treated as a linear triad of point charges with zero monopole and dipole moments and nonzero quadrupole moment. We demonstrate that binding energies and radii of quadrupolar anions strictly follow the scaling laws for two-body halo systems. Contrary to the case of dipolar anions, ground-state band of quadrupolar anions smoothly extend into the continuum, and many rotational bands could be identified above the detachment threshold. We study the evolution of a bound state of an anion as it dives into the continuum at a critical quadrupole moment and we show that the associated critical exponent is $\ensuremath{\alpha}=2$. Everything considered, quadrupolar anions represent a perfect laboratory for the studies of marginally bound open quantum systems.

Excess Electrons Bound to Molecular Systems with a Vanishing Dipole but Large Molecular Quadrupole

Electron attachment properties of covalent molecules and ion clusters with vanishing dipole moments but large quadrupoles are studied with coupled cluster ab initio methods. Selection of the molecules studied is driven by two goals, finding a paradigm quadrupole-bound anion and investigating whether there is a correlation between the magnitude of the molecular quadrupole and the vertical attachment energy. Out of all examined species, only the ion clusters and four of the covalent molecules are found to support bound anions. The shapes and spatial extents of the associated excess electron distributions are qualitatively and quantitatively characterized, respectively. Two of the four covalent systems are especially promising as paradigm systems because of advantageous trade-offs regarding the number of isomers and conformers as well as synthetic closeness to commercial sources. No correlation was found between the vertical attachment energy and molecular quadrupole in an analysis that included the newly identified bound anions, those molecules, which were found not to support bound anions, and succinonitrile, which had been studied before. Moreover, there is clearly no such thing as a "critical quadrupole moment". There are, however, very strong electron correlation effects involved in the binding of the excess electrons, and similar to succinonitrile, for five out of six anions identified here, the molecular quadrupole of the neutral itself is too weak to bind an excess electron, and electron correlation in the form of dynamic polarization is required to do so.

Quadrupole-bound anions: Efficacy of positive versus negative quadrupole moments

A pseudopotential method is utilized to study the critical stability of model anions formed by long-range quadrupolar molecular potentials. Results indicate that critical quadrupole moments of simple point-charge triads do not serve well as predictors of real quadrupole-bound anions of systems with negative moments.

Infrared spectroscopy of mass-selected neutral molecular systems without chromophore: the formamide monomer and dimer

The paper presents IR spectroscopic data and theoretical frequency calculations, in the C–H and N–H stretch region, on jet-cooled formamide molecules and dimers. By using dipole-bound or quadrupole-bound anion formation, one is able to monitor IR absorption in the neutral beam on mass-selected species. For isolated formamide, resonant IR excitation leads to autodetachment of the excess electron in the dipole-bound anion. For the formamide dimer, the IR spectrum is characteristic from the cyclic dimer, with two neighbouring bonded N–H stretches and a complex spectrum with several lines and a broad absorption band in the C–H region absorption, as for the cyclic formic acid dimer. In this double H-bond configuration, IR absorption cannot lead to vibrational predissociation but it probably produces hot neutral dimers with large-amplitude intermolecular motions that reinforce autodetachment of the nascent weakly bound anions. Thus, the present original IR spectroscopic technique, which allows for rigorous mass-selection of the neutrals, seems to be relevant for any polar neutral species.

Finite-size scaling for critical conditions for stable quadrupole-bound anions.

We present finite-size scaling calculations of the critical parameters for binding an electron to a finite linear quadrupole field. This approach gives very accurate results for the critical parameters by using a systematic expansion in a finite basis set. The model Hamiltonian consists of a charge Q located at the origin of the coordinates and k charges -Q/k located at distances R(i), i=1, em leader,k. After proper scaling of distances and energies, the rescaled Hamiltonian depends only on one free parameter q=QR. Two different linear charge configurations with q>0 and q<0 are studied using basis sets in both spherical and prolate spheroidal coordinates. For the case with q>0, the finite size scaling calculations give an extrapolated critical value of q(c)=1.469 70+/-0.000 05 a.u. by using a basis set with prolate spheroidal coordinates. For the quadrupole case with q<0, we obtained an extrapolated critical value of mid R:q(c)mid R:=3.982 51+/-0.000 01 a.u. for stable quadrupole bound anions. The corresponding critical exponent for the ground state energy alpha=1.9964+/-0.0005, with E approximately (q-q(c))(alpha).

Theoretical study of the quadrupole-bound anion (BeO) 2−

The global minimum on the potential energy surface of (BeO) 2 −, calculated at the coupled-cluster level of theory with single, double, and non-iterative triple excitations, corresponds to a rhombic D 2h structure, which may be considered as a quadrupole-bound anion. The rhombic isomer is separated by a C s symmetry transition state from the linear isomer and the energy barrier amounts to 15.4 kcal/mol. The energies of the D 2h and C ∞v anionic isomers differ by 6.2 kcal/mol. The vertical electron detachment energies amount to 8903 and 23847 cm −1 (1.10 and 2.96 eV) for the rhombic and linear anion, respectively.

Neutral and negatively-charged formamide, N-methylformamide and dimethylformamide clusters

The structure and low energy electron attachment properties of small clusters of formamide, N-methylformamide and dimethylformamide have been studied. The experimental technique used is Rydberg electron transfer (RET) between laser-excited atoms and the molecular systems. The richness of hydrogen bonding possibilities of these three highly polar molecules leads to very different structures and resultant dipoles or quadrupoles which we determine by means of an empirical model. A corresponding wide variety of cluster anions is observed and interpreted, ranging from dipole-bound or quadrupole-bound anions in their ground state or first excited state to valence-type anions.