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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)

A weakly bound complex usually has multiple structural isomers with small energy differences. The sophisticated ab initio calculations are the main workhorse for providing theoretical results of different isomers. In contrast, the experimental determination of the energy difference is very rare. We report the energy-difference measurement of a model complex: salt-water complex NaCl(H

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.

Methane activation by transition metals is of fundamental interest and practical importance, as this process is extensively involved in the natural gas conversion to fuels and value-added chemicals. While single-metal centers have been well recognized as active sites for methane activation, the active center composed of two or more metal atoms is rarely addressed and the detailed reaction mechanism remains unclear. Here, by using state-of-the-art time-of-flight mass spectrometry, cryogenic anion photoelectron imaging spectroscopy, and quantum-chemical calculations, the cooperation of the two Ta atoms in a dinuclear carbide cluster Ta2C4– for methane activation has been identified. The C–H bond activation takes place predominantly around one Ta atom in the initial stage of the reaction and the second Ta atom accepts the delivered H atom from the C–H bond cleavage. The well-resolved vibrational spectra of the cryogenically cooled anions agree well with theoretical simulations, allowing the clear characteriz...

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 H

Molecular conformation is important in chemistry and biochemistry. Conformers connected by low energy barriers can only be observed at low temperatures and are difficult to be separated. Here we report a new method to obtain conformation-selective spectroscopic information about dipolar molecular radicals via dipole-bound excited states of the corresponding anions cooled in a cryogenic ion trap. We observed two conformers of cold 3-hydroxyphenoxide anions [m center dot HO(C6H4)O-] in high-resolution photoelectron spectroscopy and measured different electron affinities, 18 850(8) and 18 917(5) cm(-1), for the syn and anti 3-hydroxyphenoxy radicals, respectively. We also observed dipole-bound excited states for m-HO(C6H4)O- with different binding energies for the two conformers due to the different dipole moments of the corresponding 3-hydroxyphenoxy radicals. Excitations to selected vibrational levels of the dipole-bound states result in conformation-selective photoelectron spectra. This method should be applicable to conformation-selective spectroscopic studies of any anions with dipolar neutral cores.

Vibrational state-selective resonant two-photon photoelectron spectra have been obtained via a triplet intermediate state ((3)Σ(-)) of AuS(-) near its detachment threshold using high-resolution photoelectron imaging of cryogenically cooled AuS(-) anions. Four vibrational levels of the (3)Σ(-) excited state are observed to be below the detachment threshold. Resonant two-photon absorptions through these levels yield vibrational state-selective photoelectron spectra to the (2)Σ final state of neutral AuS with broad and drastically different Franck-Condon distributions, reflecting the symmetries of the vibrational wave functions of the (3)Σ(-) intermediate state. The (3)Σ(-) excited state is spin-forbidden from the (1)Σ(+) ground state of AuS(-) and is accessed due to strong relativistic effects. The nature of the (3)Σ(-) excited state is confirmed by angular distributions of the photoelectron images and quantum calculations.

It was believed that the rhenium anion Re– was not stable, just like Mn–. We report the observation of Re– in the laser ablation ion source and the further confirmation via the high-resolution photoelectron spectra of Re–. The ground state of Re– ions is 5d66s2 5D4. The electron affinity of rhenium is determined to be 487.13(51) cm–1 or 60.396(63) meV.