Slow Electron Velocity-map Imaging Research Articles

Vibrational assignments and energy analyses of 3,4-difluorophenylacetylene using resonance-enhanced multiphoton ionization and slow electron velocity-map imaging techniques

Here, we report spectroscopic investigations of 3,4-difluorophenylacetylene applying two-color resonant two-photon ionization (2C-R2PI) and slow electron velocity-map imaging (SEVI) techniques. With the assistance of density functional theory (DFT) calculations, vibrational modes of the S0 neutral ground state, S1 first electronic excited state, and D0 cationic ground state were assigned. The adiabatic excitation energy of the S1 ← S0 electronic transition was determined to be 35639 ± 5 cm−1 from the resonance-enhanced multiphoton ionization (REMPI) spectroscopy. Additionally, the adiabatic ionization potential was found to be 72398 ± 5 cm−1 based on the SEVI spectra.

Energy Levels and Transition Rates for Laser Cooling Os− and a General Approach to Produce Cold Atoms and Molecules

High-resolution photoelectron energy spectra of osmium anions are obtained using the slow-electron velocity-map imaging method. The energy levels of excited states 4 F 7/2, 4 F 5/2 and 4 F 3/2 of Os− are determined to be 148.730(13), 155.69(15), and 176.76(13) THz [or 4961.09(41), 5193.4(49), and 5896.1(42) cm−1], respectively. The lifetime of the opposite-parity excited state is determined to be 201(10) μs using a cold ion trap, about 15 times shorter than the previous result 3(1) ms. Our high-level multi-configuration Dirac–Hartree–Fock calculations yield a theoretical lifetime 527 μs. Our work shows that the laser cooling rate of Os− is as fast as that of Th−. The advantages of Os− are its near-IR range cooling transition and simple electronic structure, which make Os− a promising candidate for laser cooling of negative ions. We propose a general approach to produce cold atoms and molecules based on the sympathetic cooling of negative ions in combination with a threshold photodetachment.

Spectroscopy of Radicals, Clusters, and Transition States Using Slow Electron Velocity-Map Imaging of Cryogenically Cooled Anions

Slow electron velocity-map imaging of cryogenically cooled anions (cryo-SEVI) is a high-resolution variant of anion photoelectron spectroscopy that has been applied with considerable success over the years to the study of radicals, size-selected clusters, and transition states for unimolecular and bimolecular reactions. Cryo-SEVI retains the versatility of conventional anion photoelectron spectroscopy while offering sub-meV resolution, thereby enabling the resolution of vibrational structure in the photoelectron spectra of complex anions. This Feature Article describes recent experiments in our laboratory using cryo-SEVI, including a new research direction in which anions are vibrationally pre-excited with an infrared laser pulse prior to photodetachment.

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.

Electron affinities in the periodic table and an example for As

Based on our previous analysis of electron affinities of atoms and structures of atomic negative ions [J. Phys. Chem. Ref. Data 51, 021502 (2022)], this review provides a concise presentation of the electron affinities of atoms. We briefly describe and compare three commonly used experimental methods for determining electron affinities to highlight their respective advantages and disadvantages. To illustrate the features of the slow electron velocity-map imaging method utilized in our current study, we conducted measurements on the electron affinity of As and excited states of its anion. The electron affinity of As was determined to be 6488.61(5) cm−1 or 0.804485(6) eV. The fine structures of As− were well resolved, with values of 1029.94(18) cm−1 or 0.12770(3) eV for 3P1 and 1343.04(55) cm−1 or 0.16652(7) eV for 3P0 above the ground state 3P2, respectively.

Electron affinity of tantalum and excited states of its anion.

The tantalum anion has the most complicated photoelectron spectrum among all atomic anions of transition elements, which was the main obstacle to accurately measure its electron affinity via the generic method. The latest experimental value of the electron affinity of Ta was 0.323(12) eV, reported by Feigerle et al. [J. Chem. Phys. 74, 1580 (1981)]. In the present work, we report the high-resolution photoelectron spectroscopy of Ta- via the slow-electron velocity-map imaging method combined with a cryogenic ion trap. The electron affinity of Ta was measured to be 2652.38(17) cm-1 or 0.328859(23) eV. Three excited states 5D1, 3P0, and 5D2 of Ta- were observed, and their energy levels were determined to be 1169.64(17) cm-1 for 5D1, 1735.9(10) cm-1 for 3P0, and 2320.1(20) cm-1 for 5D2 above the ground state 5D0, respectively.

Anion Resonances and Photoelectron Spectroscopy of the Tetracenyl Anion.

The photoelectron spectroscopy of the tetracenyl anion using slow electron velocity-map imaging (SEVI) of cryogenically cooled ions is presented. The total photodetachment yield as a function of photon energy is used to reveal a rich manifold of anion excited states above the detachment threshold. The lowest energy anionic resonance has a sufficiently long lifetime to yield a vibrationally resolved absorption spectrum that can be directly compared with theoretical predictions. Excitation of this state mostly results in electron detachment via thermionic emission. The total photodetachment yield spectrum is used to select photon wavelengths that minimize the indirect detachment signal to allow acquisition of vibrationally resolved photoelectron spectra that can inform on the neutral tetracenyl radical. Assignment of spectral features corresponding to the ground and first excited state of the neutral 12-tetracenyl isomer is made with the aid of Franck-Condon simulations. This yields adiabatic electron affinity and term energies that differ significantly from the previously reported values. Weak features corresponding to the ground state of the minor 2-teracenyl and 1-tetracenyl isomers are also identified, which allows for the experimental determination of their electron affinities for the first time.

Electron affinity of uranium and bound states of opposite parity in its anion

The electronic structures of actinide systems are extremely complicated because of strong electron correlations and relativistic effects. The atomic actinide anion poses even more challenges for experimental and theoretical investigations due to the extra loosely bound electron. In this work, we report the electronic structure of ${\mathrm{U}}^{\ensuremath{-}}$ using the slow-electron velocity-map imaging method. The electron affinity of U was measured to be 314.97(9) meV. Two excited states of ${\mathrm{U}}^{\ensuremath{-}}$ were observed and their energies were determined to be 84(11) and 160(12) meV above its ground state, respectively. The present study provides convincing evidence that the transition between the first excited state and the ground state of ${\mathrm{U}}^{\ensuremath{-}}$ is electric dipole (E1) allowed.

Accurate quantum dynamics simulation of the photodetachment spectrum of the nitrate anion (NO3 -) based on an artificial neural network diabatic potential model.

The photodetachment spectrum of the nitrate anion (NO3 -) is simulated from first principles using wavepacket quantum dynamics propagation and a newly developed accurate full-dimensional fully coupled five state diabatic potential model. This model utilizes the recently proposed complete nuclear permutation inversion invariant artificial neural network diabatization technique [D. M. G. Williams and W. Eisfeld, J. Phys. Chem. A 124, 7608 (2020)]. The quantum dynamics simulations are designed such that temperature effects and the impact of near threshold detachment are taken into account. Thus, the two available experiments at high temperature and at cryogenic temperature using the slow electron velocity-map imaging technique can be reproduced in very good agreement. These results clearly show the relevance of hot bands and vibronic coupling between the X̃ 2A2 ' ground state and the B̃ 2E' excited state of the neutral radical. This together with the recent experiment at low temperature gives further support for the proper assignment of the ν3 fundamental, which has been debated for many years. An assignment of a not yet discussed hot band line is also proposed.

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.

Experimental and theoretical study on p-chlorofluorobenzene in the S, S1 and D states

The geometric structures and vibration frequencies of para-chlorofluorobenzene (p-ClFPh) in the first excited state of neutral and ground state of cation were investigated by resonance-enhanced multiphoton ionization and slow electron velocity-map imaging. The infrared spectrum of S0 state and absorption spectrum for S1 ← S0 transition in p-ClFPh were also recorded. Based on the one-color resonant two-photon ionization spectrum and two-color resonant two-photon ionization spectrum, we obtained the adiabatic excited-state energy of p-ClFPh as 36302±4 cm−1. In the two-color resonant two-photon ionization slow electron velocity-map imagin spectra, the accurate adiabatic ionization potential of p-ClFPh was extrapolated as 72937±8 cm−1 via threshold ionization measurement. In addition, Franck-Condon simulation was performed to help us confidently ascertain the main vibrational modes in the S1 and D0 states. Furthermore, the mixing of vibrational modes between S0 → S1 and S1 → D0 has been analyzed.

Accurate electron affinity of atomic cerium and excited states of its anion**Project supported by the National Natural Science Foundation of China (Grant Nos. 91736102 and 11974199) and the National Key R&D Program of China (Grant No. 2018YFA0306504).

Electron affinities (EA) of most lanthanide elements still remain unknown owing to their relatively lower EA values and the fairly complicated electronic structures. In the present work, we report the high-resolution photoelectron spectra of atomic cerium anion Ce− using the slow electron velocity-map imaging method in combination with a cold ion trap. The electron affinity of Ce is determined to be 4840.62(21) cm−1 or 0.600160(26) eV. Moreover, several excited states of Ce− (4H9/2, 4I9/2, 2H9/2, 2G9/2, 2G7/2, 4H13/2, 2F5/2, and 4I13/2) are observed.

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.

Comment on “Measurement of the electron affinity of the lanthanum atom”

The electron affinity of the lanthanum atom was recently measured by slow-electron velocity map imaging in a photodetachment experiment [Y. Lu et al., Phys. Rev. A 99, 062507 (2019)]. Several detachment threshold energies have been measured, which correspond to different energy levels of the initial ion and/or final atom. Only one measurement, however, has been exploited to determine the electron affinity. Applying the ordinary spectroscopic method to the complete set of data presented by the authors, one obtains a slightly different, more precise and more consistent value of the electron affinity of La: $449\phantom{\rule{0.16em}{0ex}}691(17)$ instead of $449\phantom{\rule{0.16em}{0ex}}697(20)\phantom{\rule{4pt}{0ex}}{\mathrm{m}}^{\ensuremath{-}1}$, i.e., $0.557\phantom{\rule{0.16em}{0ex}}546(20)$ instead of $0.557\phantom{\rule{0.16em}{0ex}}553(25)\phantom{\rule{4pt}{0ex}}\mathrm{eV}$.

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 β 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.

Accurate electron affinity of lanthanum atom

SynopsisAtomic lanthanum anion La− is the best candidate for laser cooling of any atomic anions by far. The previous theoretical studies showed that La− has very a complicated electronic structure, which cannot be well resolved by the traditional photoelectron spectroscopy. In the present work, we used the slow-electron velocity-map imaging method in combination with an ion trap to measure the electronic structure of La−. The electron affinity of La is accurately determined to be 4496.97(20) cm−1 or 0.557553(25) eV.

Vibronic structure and predissociation dynamics of 2-methoxythiophenol (S1): The effect of intramolecular hydrogen bonding on nonadiabatic dynamics.

Vibronic spectroscopy and the S-H bond predissociation dynamics of 2-methoxythiophenol (2-MTP) in the S1 (ππ*) state have been investigated for the first time. Resonant two-photon ionization and slow-electron velocity map imaging (SEVI) spectroscopies have revealed that the S1-S0 transition of 2-MTP is accompanied with the planar to the pseudoplanar structural change along the out-of-plane ring distortion and the tilt of the methoxy moiety. The S1 vibronic bands up to their internal energy of ∼1000 cm-1 are assigned from the SEVI spectra taken via various S1 vibronic intermediate states with the aid of ab initio calculations. Intriguingly, Fermi resonances have been identified for some vibronic bands. The S-H bond breakage of 2-MTP occurs via tunneling through an adiabatic barrier under the S1/S2 conical intersection seam, and it is followed by the bifurcation into either the adiabatic or nonadiabatic channel at the S0/S2 conical intersection where the diabatic S2 state (πσ*) is unbound with respect to the S-H bond elongation coordinate, giving the excited (Ã) or ground (X̃) state of the 2-methoxythiophenoxy radical, respectively. Surprisingly, the nonadiabatic transition probability at the S0/S2 conical intersection, estimated from the velocity map ion images of the nascent D fragment from 2-MTP-d1 (2-CH3O-C6H4SD) at the S1 zero-point energy level, is found to be exceptionally high to give the X̃/Ã product branching ratio of 2.03 ± 0.20, which is much higher than the value of ∼0.8 estimated for the bare thiophenol at the S1 origin. It even increases to 2.33 ± 0.17 at the ν45 2 mode (101 cm-1) before it rapidly decays to 0.69 ± 0.05 at the S1 internal energy of about 2200 cm-1. This suggests that the strong intramolecular hydrogen bonding of S⋯D⋯OCH3 in 2-MTP at least in the low S1 internal energy region should play a significant role in localizing the reactive flux onto the conical intersection seam. The minimum energy pathway calculations (second-order coupled-cluster resolution of the identity or time-dependent-density functional theory) of the adiabatic S1 state suggest that the intimate dynamic interplay between the S-H bond cleavage and intramolecular hydrogen bonding could be crucial in the nonadiabatic surface hopping dynamics taking place at the conical intersection.

Measurement of the electron affinity of the lanthanum atom

Atomic lanthanum anion ${\mathrm{La}}^{\ensuremath{-}}$ is the best candidate for laser cooling of any atomic anions found so far. The bound-bound electric dipole transitions of ${\mathrm{La}}^{\ensuremath{-}}$ have been identified and measured. Theoretical studies have shown that ${\mathrm{La}}^{\ensuremath{-}}$ has a very complicated electronic structure, which cannot be well resolved by the traditional photoelectron spectroscopy. In the present work, we report high-resolution photoelectron spectroscopy of ${\mathrm{La}}^{\ensuremath{-}}$ via the slow-electron velocity-map imaging method in combination with an ion trap. The electron affinity of La was determined to be $4496.97(20)\phantom{\rule{0.16em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ or 0.557 553(25) eV. In addition, the energy levels of ${\mathrm{La}}^{\ensuremath{-}}$, $^{3}F_{3}^{e}$, $^{3}F_{4}^{e}$, $^{1}D_{2}^{e}$, $^{1}D_{2}^{o}$, $^{3}P_{0}^{e}$, $^{3}P_{1}^{e}$, and $^{3}P_{2}^{e}$, were also determined.

Measurement of electron affinity of atomic lutetium via the cryo-SEVI Method

Electron affinities (EAs) of most lanthanide elements still remain unknown due to their relatively low EA values. In the present work, the cryogenically controlled ion trap is used for accumulating atomic lutetium anion Lu−, which makes the measurement of electron affinity of lutetium become practicable. The high-resolution photoelectron spectra of Lu− are obtained via the slow-electron velocity-map imaging method. The electron affinity of Lu is determined to be 1926.2(50) cm−1 or 0.23882(62) eV. In addition, two excited states of Lu− are observed.

Photoelectron spectra of Al2O2- and Al3O3-via slow electron velocity-map imaging.

High-resolution photoelectron spectra of cryogenically-cooled Al2O2- and Al3O3- cluster anions are obtained using slow electron velocity-map imaging. These spectra show vibrationally-resolved detachment from the (X[combining tilde]2B3u) ground state of Al2O2- to the X[combining tilde]1Ag and ã3B3u neutral electronic states, giving an electron affinity of 1.87904(4) eV for neutral Al2O2 and a term energy of 0.4938(4) eV for the triplet excited state. Additionally, there is evidence for autodetachment from photoexcited anions as well as influences from vibronic coupling between excited states of the neutral Al2O2 cluster. Detachment from both the "kite" and "book" isomers of Al3O3- is observed, yielding electron affinities of 2.0626(4) and 2.792(3) eV for the corresponding neutral isomers. Experiments carried out at different anion temperatures suggest that the two anionic isomers are nearly isoenergetic but clearly identify the kite isomer as the global minimum structure, in contrast to prior studies. This finding is supported by density functional theory calculations, which show that the relative ordering of the anion isomers is sensitive to basis set size; calculations for the anion isomers at the B3LYP/aug-cc-pVQZ level find the kite isomer to lie 0.011 eV below the book isomer.