Observation of bound valence excited electronic states of deprotonated 2-hydroxytriphenylene using photoelectron, photodetachment, and resonant two-photon detachment spectroscopy of cryogenically cooled anions.

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh-), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh- anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh- anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh-, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3 eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh- would be an interesting system for pump-probe experiments to unravel the dynamics of the excited states of this complex PAH anion.

On the electronic structure and spin-orbit coupling of BiB from photoelectron imaging of cryogenically-cooled BiB- anion.

We report a study on the electronic structure and chemical bonding of the BiB molecule using high-resolution photoelectron imaging of cryogenically cooled BiB- anion. By eliminating all the vibrational hot bands, we can resolve the complicated detachment transitions due to the open-shell nature of BiB and the strong spin-orbit coupling. The electron affinity of BiB is measured to be 2.010(1) eV. The ground state of BiB- is determined to be 2Π(3/2) with a σ2π3 valence electron configuration, while the ground state of BiB is found to be 3Σ-(0+) with a σ2π2 electron configuration. Eight low-lying spin-orbit excited states [3Σ-(1), 1Δ(2), 1Σ+(0+), 3Π(2), 3Π(1), 1Π(1)], including two forbidden transitions, [3Π(0-) and 3Π(0+)], are observed for BiB as a result of electron detachment from the σ and π orbitals of BiB-. The angular distribution information from the photoelectron imaging is found to be critical to distinguish detachment transitions from the σ or π orbital for the spectral assignment. This study provides a wealth of information about the low-lying electronic states and spin-orbit coupling of BiB, demonstrating the importance of cryogenic cooling for obtaining well-resolved photoelectron spectra for size-selected clusters produced from a laser vaporization cluster source.

Photoelectron imaging of cryogenically cooled BiO- and BiO2 - anions.

The advent of ion traps as cooling devices has revolutionized ion spectroscopy as it is now possible to efficiently cool ions vibrationally and rotationally to levels where truly high-resolution experiments are now feasible. Here, we report the first results of a new experimental apparatus that couples a cryogenic 3D Paul trap with a laser vaporization cluster source for high-resolution photoelectron imaging of cold cluster anions. We have demonstrated the ability of the new apparatus to efficiently cool BiO- and BiO2 - to minimize vibrational hot bands and allow high-resolution photoelectron images to be obtained. The electron affinities of BiO and BiO2 are measured accurately for the first time to be 1.492(1) and 3.281(1) eV, respectively. Vibrational frequencies for the ground states of BiO and BiO2, as well as those for the anions determined from temperature-dependent studies, are reported.

Polarization of Valence Orbitals by the Intramolecular Electric Field from a Diffuse Dipole-Bound Electron.

The diffuse electron in a dipole-bound state is spatially well separated from the valence electrons and is known to have negligible effects on the dipole-bound state's molecular structure. Here, we show that a dipole-bound state is observed in deprotonated 4-(2-phenylethynyl)-phenoxide anions, 348 cm-1 below the anion's detachment threshold. The photodetachment of the dipole-bound electron is observed to accompany a simultaneous shakeup process in valence orbitals in this aromatic molecular anion. This shakeup process is due to configuration mixing as a result of valence orbital polarization by the intramolecular electric field of the dipole-bound electron. This observation suggests that dipole-bound anions can serve as a new platform to probe how oriented electric fields influence the valence electronic structure of polyatomic molecules.

High-resolution photoelectron imaging of MnB3 -: Probing the bonding between the aromatic B3 cluster and 3d transition metals.

The B3 triangular unit is a fundamental bonding motif in all boron compounds and nanostructures. The isolated B3 - cluster has a D3h structure with double σ and π aromaticity. Here, we report an investigation of the bonding between a B3 cluster and a 3d transition metal using high-resolution photoelectron imaging and computational chemistry. Photoelectron spectra of MnB3 - are obtained at six different photon energies, revealing rich vibrational information for the ground state detachment transition. The electron affinity of MnB3 is determined to be 1.6756(8) eV, and the most Franck-Condon-active mode observed has a measured frequency of 415(6) cm-1 due to the Mn-B3 stretch. Theoretical calculations show that MnB3 - has a C2v planar structure, with Mn coordinated to one side of the triangular B3 unit. The ground states of MnB3 - (6B2) and MnB3 (5B2) are found to have high spin multiplicity with a significant decrease in the Mn-B bond distances in the neutral due to the detachment of an Mn-B3 anti-bonding electron. The Mn atom is shown to have weak interactions with the B3 unit, which maintains its double aromaticity with relatively small structural changes from the bare B3 cluster. The bonding in MnB3 is compared with that in 5d MB3 clusters, where the strong metal-B3 interactions strongly change the structures and bonding in the B3 moiety.

The nature of the chemical bonding in 5d transition-metal diatomic borides MB (M = Ir, Pt, Au).

Boron can form strong bonds with transition metals in diatomic metal borides (MB), but the nature of the chemical bonding has not been well understood. Recently, a quadruple bond was discovered in Rh≣B, consisting of two σ bonds formed between the Rh 4dz2 and B 2s/2p orbitals and two π bonds between the Rh 4dxz/4dyz and the B 2px/2py orbitals. The bonding between the 5d transition metals and boron is expected to be even stronger. Here, we report an investigation on the electronic structure and chemical bonding of the 5d transition metal diatomic borides (IrB, PtB, and AuB) using high-resolution photoelectron imaging on the corresponding anions (MB-) and theoretical calculations. Vibrationally resolved photoelectron spectra are obtained for all three anions, and the electron affinities are measured for IrB, PtB, and AuB to be 1.995(1), 2.153(3), and 0.877(6) eV, respectively. It is found that the weakly anti-bonding 3σ molecular orbital (mainly of M 6s and B sp characters) is singly occupied in IrB (3Δ) and PtB (2Σ+), resulting in a bond order of three and half for these two diatomic borides. The 3σ orbital is doubly occupied in AuB (1Σ+), giving rise to a weak triple bond. Despite the lower bond order, the bonding in IrB and PtB is only slightly weaker than that in RhB due to the more favorable interactions between the M 5d orbitals and the B sp orbitals.

MnB6-: An Open-Shell Metallaboron Analog of 3d Metallabenzenes.

We report a study of the structure and bonding of a transition-metal-doped boron cluster, MnB6-, using high-resolution photoelectron imaging and quantum chemical calculations. Vibrationally resolved photoelectron spectra indicate a significant geometry change between the anionic and neutral ground states of MnB6. The electron affinity of MnB6 is measured to be 2.4591(5) eV, and vibrational frequencies for five of its vibrational modes were determined. The experimental data are combined with theoretical calculations to determine the structure and bonding of MnB6-, which is found to be planar with a B-centered hexagonal structure (C2v symmetry) and a quintet spin state (5A2). Nuclear-independent chemical shift calculations indicate that MnB6- is aromatic. Molecular orbital analyses reveal that MnB6- contains three π orbitals, one of which is singly occupied. Hence, MnB6- can be considered as an open-shell metallaboron analog of 3d metallabenzenes.

Observation of Möbius Aromatic Planar Metallaborocycles.

Möbius aromaticity was developed for twisted annulenes with electron counting rules opposite to those of Hückel aromaticity. The introduction of transition metals makes it possible for planar cyclic systems to exhibit Möbius aromaticity. Here we report the first planar monocyclic metallaboron systems with Möbius aromaticity. The structures and bonding of two rhenium-boride clusters are studied by high-resolution photoelectron imaging and ab initio calculations. The ReB3- cluster is shown to have a near-pyramidal structure, while ReB4- is found to be a planar pentagonal ring. Chemical bonding analyses show that both ReB4- and ReB4 possess four delocalized π-electrons, including two π-electrons in an orbital of Möbius topology. NICS calculations reveal strong aromatic characters in ReB4- and ReB4, consistent with the 4n electron counting rule for Möbius aromaticity.

Observation of Four-Fold Boron-Metal Bonds in RhB(BO-) and RhB.

The maximum bond order between two main-group atoms was known to be three. However, it has been suggested recently that there is quadruple bonding in C2 and analogous eight-valence electron species. While the quadruple bond in C2 has aroused some debates, an interesting question is: are main-group elements capable of forming quadruple bonds? Here we use photoelectron spectroscopy and computational chemistry to probe the electronic structure and chemical bonding in RhB2O- and RhB- and show that the boron atom engages in quadruple bonding with rhodium in RhB(BO)- and neutral RhB. The quadruple bonds consist of two π-bonds formed between the Rh 4dxz/4dyz and B 2px/2py orbitals and two σ-bonds between the Rh 4dz2 and B 2s/2pz orbitals. To confirm the quadruple bond in RhB, we also investigate the linear Rh≡B-H+ species and find a triple bond between Rh and B, which has a longer bond length, lower stretching frequency, and smaller bond dissociation energy in comparison with that of the Rh≣B quadruple bond in RhB.

ReB6-: A Metallaboron Analog of Metallabenzenes.

Metallabenzenes are a class of molecules in which a CH unit in benzene is replaced by a functionalized transition-metal atom. While all-boron analogues of aromatic and antiaromatic hydrocarbons are well-known, there have not been any metallaboron analogs. We have produced and investigated two metal-doped boron clusters, ReB6- and AlB6-, using high-resolution photoelectron imaging and quantum chemical calculations. Vibrationally resolved photoelectron spectra have been obtained and compared with the theoretical results. The ReB6- cluster is found to be perfectly planar with a B-centered hexagonal structure (C2v, 1A1), while AlB6- is known to have a similar structure, but with a slightly out-of-plane distortion (Cs, 1A'). Chemical bonding analyses show that the closed-shell ReB6- is doubly σ- and π-aromatic, while AlB6- is known to be σ-aromatic and π-antiaromatic. The out-of-plane distortion in AlB6- is due to antiaromaticity, akin to the out-of-plane distortion of the prototypical antiaromatic cyclooctatetraene. The π-bonding in ReB6- is compared with that in both benzene and rhenabenzene [(CO)4ReC5H5], and remarkable similarities are found. Hence, ReB6- can be viewed as the first metallaboron analog of metallabenzenes and it may be viable for syntheses with suitable ligands.

High-Resolution Photoelectron Imaging of IrB3 - : Observation of a π-Aromatic B3 + Ring Coordinated to a Transition Metal.

In a high-resolution photoelectron imaging and theoretical study of the IrB3 - cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B3 ring coordinated with the Ir atom. The isomer with the higher EA consists of a B3 ring with a bridge-bonded Ir atom (Cs , 2 A'), and the second isomer features a tetrahedral structure (C3v , 2 A1 ). The neutral tetrahedral structure was predicted to be considerably more stable than all other isomers. Chemical bonding analysis showed that the neutral C3v isomer involves significant covalent Ir-B bonding and weak ionic bonding with charge transfer from B3 to Ir, and can be viewed as an Ir-(η3 -B3 + ) complex. This study provides the first example of a boron-to-metal charge-transfer complex and evidence of a π-aromatic B3 + ring coordinated to a transition metal.

Probing the coupling of a dipole-bound electron with a molecular core.

A dipolar molecule can weakly bind an electron in a diffuse orbital. However, the spin-orbit coupling between this weakly bound electron and the electrons in the molecular core is not known. Here we probe this coupling using the linear C2P- anion with the 3Σ+ ground state, which possesses dipole-bound excited states because neutral C2P (2Π) has a sufficiently large dipole moment. Photodetachment spectroscopy and resonant photoelectron spectroscopy are used to probe the nature of the dipole-bound states. Two dipole-bound excited states are observed with a binding energy of 37 cm-1, corresponding to the two spin-orbit states of neutral C2P (2Π1/2 and 2Π3/2). The current study demonstrates that the weakly bound electron in the dipole-bound excited states of C2P- is not spin-coupled to the electrons in the C2P core and can be considered as a quasi-free electron.

High resolution photoelectron imaging of boron-bismuth binary clusters: Bi2Bn - (n = 2-4).

Bismuth boride is a heavy member of the III-V semiconductors. Although there have been some theoretical interests in this material, it has not been synthesized experimentally. Here, we report a high-resolution photoelectron imaging study on a series of boron-bismuth binary clusters, Bi2Bn - (n = 2-4), produced by laser vaporization of a B/Bi mixed target. Vibrationally resolved photoelectron spectra are obtained for all three clusters, and the measured vibrational and electronic information is used to compare with theoretical calculations to understand their structures and bonding. Bi2B2 - is found to be linear (D∞h, 2Πg) with a B2 unit and two terminal Bi atoms, while Bi2B3 - is found to be planar (C2v, 1A1), consisting of a B3 triangle with two bridging Bi atoms. Interestingly, the spectra of Bi2B4 - reveal two co-existing isomers; both are found to be planar and contain a rhombus B4 unit with two bridging Bi atoms in a trans (C2h, 2Au) and cis (C2v, 2B1) fashion separated only by 0.03 eV in energy. The interactions between the two Bi atoms and the Bn motifs are understood using chemical bonding analyses. This study shows that the Bi-B bonding is weak enough so that the Bn units maintain their structural integrity with the Bi atoms bonded to the cluster periphery only.

Characteristics of Ice Impedance Recorded From a Ring Electrode Placed at the Anterior Surface of the Cryoballoon: Novel Approach to Define Ice Formation and Pulmonary Vein Isolation.

BACKGROUND: The success of cryoablation of the pulmonary vein isolation (PVI) is dependent on transmural and circumferential ice formation. We hypothesize that rising impedance recorded from a ring electrode placed 2 mm from the cryoballoon signifies ice formation covering the balloon surface and indicates ice expansion. The impedance level enables titration of the cryoapplication time to avoid extracardiac damage while ensuring PVI. METHODS AND RESULTS: In 12 canines, a total of 57 pulmonary veins were targeted for isolation. Two cryoapplications were delivered per vein with a minimum of 90 and maximum of 180-second duration. Cryoapplication was terminated on reaching a 500 Ω change from baseline. Animals recovered 38±6 days post-procedure, and veins were assessed electrically for isolation. Heart tissue was histologically analyzed. Extracardiac structures were examined for damage. PVI was achieved in 100% of the veins if the impedance reached 500 Ω in <90 seconds with freeze time of 90 seconds. When 500 Ω was reached >90 to 180 seconds (142.60±29.3 seconds), 90% PVI was achieved. When the final impedance was between 200 and 500 Ω with 180 seconds of freeze time, PVI was achieved in 86.8%. For impedance of <200 Ω, PVI was achieved in 14%. No extracardiac damage was recorded. CONCLUSIONS: Impedance rise of 500 Ω at <90 seconds with freeze time of 90 seconds resulted in 100% PVI. Impedance measurements from the nose of the balloon is a direct measure of ice formation on the balloon. It provides real-time feedback on the quality of the ablation and defines the cryoapplication termination time based on ice formation, limiting ice expansion to extracardiac tissues.

Novel dyeless and fluoro-less approach to cryoballoon pulmonary vein occlusion assessment.

BACKGROUND: Pulmonary vein (PV) occlusion is essential for PV isolation (PVI) using the cryoballoon. Currently occlusion is arbitrarily determined using fluoroscopy and contrast media. This study aimed to create an objective measure without utilizing excessive fluoroscopy and using no contrast media. OBJECTIVE: To ensure PV occlusion without fluoroscopy and contrast dye. METHODS: In 4 in vivo hearts 113 PV occlusions were tested with a 50% cold dye saline mix at 4°C. Occlusions were rated Good, Fair, and Poor by dye dissipation seen via fluoroscopy and correlated to temperature profiles recorded concurrently. Using these temperature profiles and no dye, cryoablations were placed in 12 additional hearts (56 unique veins, 126 occlusions). Two 180-second cryoablation applications were placed per vein with occlusion testing in between. PVI was defined by electrophysiology mapping, gross pathology, and histology after ≥4 weeks recovery. RESULTS: Dye results were as follows: With Good, Fair, and Poor the maximal postinjection PV temperature dropped (ΔT) by 6.2 ± 4.2°C, 5.1 ± 3.7°C, and 2.4 ± 2.0°C. At 5 seconds post nadir temperature, injection temperature recovered 18% ± 14%, 36% ± 23%, and 50% ± 33%. Console thaw time to 0°C was 11.5 ± 4.8 seconds, 8.5 ± 2.1 seconds, and 4.3 ± 1.3 seconds. Success rate for PVI was 100%, 97%, and 0%. With no dye: ΔT: 7.7 ± 4.4°C, 5.8 ± 5.0°C, and 3.4 ± 2.3°C; % recovery at 5 seconds: 15% ± 12%, 31% ± 23%, 45% ± 30%; thaw time to 0°C: 11.9 ± 4.8 seconds, 10.5 ± 5.2 seconds, 6.0 ± 2.8 seconds; success rate: 97%, 91%, and 10%. CONCLUSION: PV occlusion profile determination using 4°C cold saline injection is an effective approach to define the occlusion grade. Quality occlusions correlate strongly with PVI success.

Communication: High precision sub-Doppler infrared spectroscopy of the HeH⁺ ion.

The hydrohelium cation, HeH(+), serves as an important benchmark for ab initio calculations that take into account non-adiabatic, relativistic, and quantum electrodynamic effects. Such calculations are capable of predicting molecular transitions to an accuracy of ~300 MHz or less. However, in order to continue to push the boundaries on these calculations, new measurements of these transitions are required. Here we measure seven rovibrational transitions in the fundamental vibrational band to a precision of ~1 MHz using the technique of Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy. These newly measured transitions are included in a fit to the rotation-vibration term values to derive refined spectroscopic constants in the v = 0 and v = 1 vibrational states, as well as to calculate rotation-vibration energy levels with high precision.