The unusual quadruple bonding of nitrogen in ThN.

Nitrogen has five valence electrons and can form a maximum of three shared electron-pair bonds to complete its octet, which suggests that its maximum bond order is three. With a joint anion photoelectron spectroscopy and quantum chemistry investigation, we report herein that nitrogen presents a quadruple bonding interaction with thorium in ThN. The quadruple Th≣N bond consists of two electron-sharing Th-N π bonds formed between the Th-6dxz/6dyz and N 2px/2py orbitals, one dative Th←N σ bond and one weak Th←N σ bonding interaction formed between Th-6dz2 and N 2s/2pz orbitals. The ThC molecule has also been investigated and proven to have a similar bonding pattern as ThN. Nonetheless, due to one singly occupied σ-bond, ThC is assigned a bond order of 3.5. Moreover, ThC has a longer bond length as well as a lower vibrational frequency in comparison with ThN.

Electron affinity of atomic scandium and yttrium and excited states of their negative ions.

The latest experimental electron affinity (EA) values of atomic scandium and yttrium were 0.189(20) and 0.308(12) eV as reported by Feigerle et al. in 1981. The measurement accuracy of these was far lower than that of other transition elements, and no conclusive result had been made on the excited states of their negative ions. In the current work, we report more accurate EA values of Sc and Y and the electronic structure of their negative ions using the slow-electron velocity-map imaging method. The EA values of Sc and Y are determined to be 0.179 378(22) and 0.311 29(22) eV, respectively. The ground state of Sc- is identified as 3d4s24p 1D2, and the ground state is 4d5s25p 1D2 for Y-. Furthermore, several excited states of Sc- and Y- are observed: Sc- (3D1) and Y- (3D1, 3D2, 3D3, 3F2, and 3F3), and their energy levels are determined to be 1131.8(28), 1210.0(13), 1362.3(30), 1467.7(26), 1747(16), and 1987(33) cm-1, respectively.

Probing Isomerization Dynamics via a Dipole-Bound State.

The observation of molecular isomerization dynamics is a long-standing goal in physical chemistry. The loosely bound electron in a dipole-bound state (DBS) can be a messenger for probing the isomerization of the neutral core. Here we study the isomerization dynamics of the salt dimer (NaCl)2 from linear to rhombic via a DBS using cryogenic photoelectron spectroscopy in combination with ab initio calculations. Although the energy level of the DBS is below the electron affinity of the linear (NaCl)2, (NaCl)2- in its DBS can autodetach due to the linear-to-rhombic isomerization. (NaCl)2- in the ground DBS has a relatively long lifetime of a few nanoseconds due to the quantum tunneling through a potential barrier during the transformation from linear to rhombic. In contrast, the vibrationally excited DBS has a much shorter lifetime on the order of picoseconds. The energy distribution of autodetachment electrons has an unexpected characteristic of the thermionic emission.

Observation of an Excited Dipole-Bound State in a Diatomic Anion.

We report the observation of σ-type and π-type excited dipole-bound states (DBSs) in cryogenically cooled potassium iodide (KI) anions for the first time. Two DBSs were observed 39.7(10) meV and 5.0(12) meV below the photodetachment threshold via the resonant two-photon detachment. The different photoelectron angular distributions and binding energies suggest that the two DBSs are of different types. The existence of one σ-type and one π-type DBS in the KI anion was also supported by the high-level ab initio theoretical calculations. The excellent agreement between experimental and theoretical results confirms the prediction that a dipolar molecule with a large enough dipole moment can have an excited DBS.

Dipole-bound and valence excited states of AuF anions via resonant photoelectron spectroscopy.

Gold fluoride is a very unique species. In this work, we reported the resonant photodetachment spectra of cryogenically cooled AuF- via the slow-electron velocity-map imaging method. We determined the electron affinity of AuF to be 17 976(8) cm-1 or 2.2287(10) eV. We observed a dipole-bound state with a binding energy of 24(8) cm-1, a valence excited state with a binding energy of 1222(11) cm-1, and a resonant state with an energy of 814(12) cm-1 above the photodetachment threshold. An unusual vibrational transition with Δn = -3 was observed in the autodetachment from the dipole-bound state. Moreover, two excited states of neutral AuF were recognized for the first time, located at 13 720(78) cm-1 and 16 188(44) cm-1 above the AuF ground state.

Accurate electron affinity of Ga and fine structures of its anions.

We report the high-resolution photoelectron spectra of negative gallium anions obtained via the slow-electron velocity-map imaging method. The electron affinity of Ga is determined to be 2429.07(12) cm-1 or 0.301 166(14) eV. The fine structures of Ga are well resolved: 187.31(22) cm-1 or 23.223(27) meV for 3P1 and 502.70(28) cm-1 or 62.327(35) meV for 3P2 above the ground state 3P0, respectively. The photoelectron angular distribution for photodetachment from Ga-(4s24p2 3P0) to Ga(4s25s 2S1/2) is measured. An unexpected perpendicular distribution instead of an isotropic distribution is observed, which is due to a resonance near 3.3780 eV.

Measurement of electron affinity of iridium atom and photoelectron angular distributions of iridium anion.

The latest electron affinity value of an iridium atom is 1.564 36(15) eV, determined via a method based on the Wigner threshold law by Bilodeau and co-workers. However, they observed a significant deviation from the Wigner threshold law in the threshold photodetachment experiment. To address this dilemma, we conducted high-resolution photoelectron spectroscopy of Ir- via the slow-electron velocity-map imaging method in combination with an ion trap. The electron affinity of Ir was measured to be 12 614.97(9) cm-1 or 1.564 057(11) eV. We find that the Wigner threshold law is still valid for the threshold photodetachment of Ir- through a p-wave fitting of the photodetachment channel Ir-5d86s23F4→Ir5d86sb4F9/2. The photoelectron angular distributions of photodetachment channels Ir-5d86s23F4→Ir5d76s2a4F9/2 and Ir-5d86s23F4→Ir5d86sb4F9/2 were also investigated. The behavior of anisotropy parameter ß indicates a strong interaction between the two channels. Moreover, the energy level 3P2 of Ir-, which was not observed in the previous works, was experimentally determined to be 4163.24(16) cm-1 above the ground state.

Candidate for Laser Cooling of a Negative Ion: High-Resolution Photoelectron Imaging of Th

Laser cooling is a well-established technique for the creation of ensembles of ultracold neutral atoms or positive ions. This ability has opened many exciting new research fields over the past 40 years. However, no negatively charged ions have been directly laser cooled because a cycling transition is very rare in atomic anions. Efforts of more than a decade currently have La^{-} as the most promising candidate. We report on experimental and theoretical studies supporting Th^{-} as a new promising candidate for laser cooling. The measured and calculated electron affinities of Th are, respectively, 4901.35(48) cm^{-1} and 4832 cm^{-1}, or 0.607 690(60) and 0.599 eV, almost a factor of 2 larger than the previous theoretical value of 0.368 eV. The ground state of Th^{-} is determined to be 6d^{3}7s^{2} ^{4}F_{3/2}^{e} rather than 6d^{2}7s^{2}7p ^{4}G_{5/2}^{o}. The consequence of this is that there are several strong electric dipole transitions between the bound levels arising from configurations 6d^{3}7s^{2} and 6d^{2}7s^{2}7p in Th^{-}. The potential laser-cooling transition is ^{2}S_{1/2}^{o}↔^{4}F_{3/2}^{e} with a wavelength of 2.6 µm. The zero nuclear spin and hence lack of hyperfine structure in Th^{-} reduces the potential complications in laser cooling as encountered in La^{-}, making Th^{-} a new and exciting candidate for laser cooling.

Ground-State Pd Anions React with H2 Much Faster than the Excited Pd Anions.

Recent advances in experimental techniques have made it relatively easy to prepare reactant cations in well-defined states of electronic excitation. Extensive studies on the role of excited states in the cation-neutral reactions have contributed significantly to our understanding of reaction kinetics and dynamics. The excited states are often more reactive than the ground state. However, the reactions involving the excited atomic anion are very rare because the negative ions usually have no bound excited states. In the present work, we report the state-specific reaction of Pd anions with H2. Surprisingly, we observed that the ground-state Pd anions react with H2 10 times faster than the excited Pd anions. The high-level calculations show that the difference is due to the reaction barrier.

Accurate electron affinity of Ti and fine structures of its anions.

The high-resolution photoelectron energy spectra of atomic titanium and its hydride anions were obtained on a slow-electron velocity-map imaging spectrometer equipped with a cold ion trap. The cold ion trap employed in the present measurement was found to be very helpful for reducing the interference from the titanium hydride anions. The electron affinity of Ti was determined to be 609.29(34) cm-1 or 75.54(4) meV. The accuracy was improved by a factor of 350 compared with the previous result. The fine structures of Ti- were clearly resolved: 70.0(12)(4F5/2), 165.2(15)(4F7/2), and 285.2(15) cm-1 (4F9/2) above its ground state 4F3/2. Moreover, the measured electron affinity and vibrational frequency of TiH can be reproduced well using the high level calculations.