Threshold Ionization Spectroscopy Research Articles

Impact of chlorine substitution on valence orbitals and ionization dynamics in 3-chloropyridine: Insights from high-resolution vacuum ultraviolet mass-analyzed threshold ionization study.

In this study, the effects of chlorine substitution on the valence orbitals and electronic states of 3-chloropyridine (3-CP) were investigated utilizing high-resolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy and computational methods. High-quality vibrational spectra were obtained from the VUV-MATI spectra of 3-CP isotopomers (35Cl and 37Cl), revealing high-quality vibrational spectra for the lowest cationic states. The adiabatic ionization energies (AIEs) of these isotopomers were accurately determined, providing detailed information about the electronic structure and ionization dynamics. Intense spectra peaks were linked with the D1 excited state of the 3-CP cation, with vibronic transitions in this state closely matching those predicted by Franck-Condon simulations. This provided insights into the cationic structure and the roles of the highest occupied molecular orbital (HOMO) and the HOMO-1. The HOMO was primarily a π orbital of the pyridine ring, while the HOMO-1 consisted of nonbonding orbitals. The AIEs suggested that meta-chlorine substitution stabilizes nonbonding orbitals less effectively than ortho substitution, indicating closely spaced electronic states in the 3-CP cation. Minor discrepancies in vibrational frequencies and intensities, particularly above 800cm-1, suggested the presence of vibronic coupling, warranting further investigation. Overall, this study provided a comprehensive understanding of the vibronic and ionization properties of 3-CP, emphasizing the influence of the position of the chlorine substitution on molecular orbitals and the value of advanced theoretical and experimental approaches for analyzing the vibrational spectra of complex molecules.

Spectroscopic and computational characterization of lanthanide-mediated bond activation of ethylamine

Ln (Ln = La and Ce) atom reactions with ethylamine are conducted in a pulsed laser vaporization supersonic molecular beam source. Dehydrogenation and association metal-containing species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln ethylimido species in the formula Ln(NC2H5) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling through multiconfiguration quasi-degenerate second-order perturbation theory for the Ce species. The MATI spectrum of lanthanum ethylimido La(NCH2CH3) has a single vibronic band system from the ionization of the doublet ground state with the La 6s1 configuration, whereas that of the cerium ethylimido Ce(NCH2CH3) displays two vibronic band system from the ionization of the two lowest-energy spin-orbit coupling states with the Ce 4f16s1 configuration. Both Ln ethylimido complexes are formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group. Two additional isomers of Ln(NC2H5) include a four-membered metallacycle Ln(NHCH2CH2) from the dehydrogenation of the amino and methyl groups and a three-membered cycle Ln(NHCHCH3) from the dehydrogenation of the amino and methylene groups. The cyclic isomers are not observed experimentally as they are not populated under the experimental conditions.

Spin-orbit coupling of electrons on separate lanthanide atoms of Pr2O2 and its singly charged cation.

Although it plays a critical role in the photophysics and catalysis of lanthanides, spin-orbit coupling of electrons on individual lanthanide atoms in small clusters is not well understood. The major objective of this work is to probe such coupling of the praseodymium (Pr) 4f and 6s electrons in Pr2O2 and Pr2O2+. The approach combines mass-analyzed threshold ionization spectroscopy and spin-orbit multiconfiguration second-order quasi-degenerate perturbation theory. The energies of six ionization transitions are precisely measured; the adiabatic ionization energy of the neutral cluster is 38 045 (5) cm-1. Most of the electronic states involved in these transitions are identified as spin-orbit coupled states consisting of two or more electron spins. The electron configurations of these states are 4f46s2 for the neutral cluster and 4f46s for the singly charged cation, both in planar rhombus-type structures. The spin-orbit splitting due to the coupling of the electrons on the separate Pratoms is on the order of hundreds of wavenumbers.

Unraveling the Conformational Preference of Morpholine: Insights from Infrared Resonant Vacuum Ultraviolet Photoionization Mass Spectroscopy.

The preference for different conformations in morpholine has a notable effect on its behavior and reactivity in organic synthesis. Herein, we explored the intricate conformational properties of morpholines through a combination of advanced mass spectrometric techniques and theoretical calculations. Notably, we employed infrared (IR) resonant vacuum ultraviolet (VUV) mass-analyzed threshold ionization spectroscopy to measure the unique vibrational spectra of the distinct conformers (Chair-Eq and Chair-Ax) in morpholine for the first time. Through precise VUV photon energy adjustments to coincide with the vibrational excitation via IR absorption, we effectively pinpointed the adiabatic ionization thresholds corresponding to the Chair-Eq (65 442 ± 4 cm-1) and Chair-Ax (65 333 ± 4 cm-1) conformers. This allowed us to accurately determine the conformational stability between the two conformers (109 ± 4 cm-1). By shedding light on the conformational properties of morpholine, this study brings far-reaching implications to the fields of organic synthesis and pharmaceutical research.

Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck-Condon Simulations.

Fluorinated organic compounds have superior physicochemical properties than general organic compounds due to the strong C-F single bond; they are widely used in medicine, biology, pesticides, and materials science. In order to gain a deeper understanding of the physicochemical properties of fluorinated organic compounds, fluorinated aromatic compounds have been investigated by various spectroscopic techniques. 2-fluorobenzonitrile and 3-fluorobenzonitrile are important fine chemical intermediates and their excited state S1 and cationic ground state D0 vibrational features remain unknown. In this paper, we used two-color resonance two photon ionization (2-color REMPI) and mass analyzed threshold ionization (MATI) spectroscopy to study S1 and D0 state vibrational features of 2-fluorobenzonitrile and 3-fluorobenzonitrile. The precise excitation energy (band origin) and adiabatic ionization energy were determined to be 36,028 ± 2 cm-1 and 78,650 ± 5 cm-1 for 2-fluorobenzonitrile and 35,989 ± 2 cm-1 and 78,873 ± 5 cm-1 for 3-fluorobenzonitrile, respectively. The density functional theory (DFT) at the levels of RB3LYP/aug-cc-pvtz, TD-B3LYP/aug-cc-pvtz, and UB3LYP/aug-cc-pvtz were used to calculate the stable structures and vibrational frequencies for the ground state S0, excited state S1, and cationic ground state D0, respectively. Franck-Condon spectral simulations for transitions of S1 ← S0 and D0 ← S1 were performed based on the above DFT calculations. The theoretical and experimental results were in good agreement. The observed vibrational features in S1 and D0 states were assigned according to the simulated spectra and the comparison with structurally similar molecules. Several experimental findings and molecular features were discussed in detail.

Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy.

Metallocenes represent one of the most important classes of organometallics with wide prospects for practical use in various fields of chemistry, materials science, molecular electronics, and biomedicine. Many applications of these metal complexes are based on their ability to form molecular ions. We report the first results concerning the changes in the molecular and electronic structure of decamethylmanganocene, Cp*2Mn, upon ionization provided by the high-resolution mass-analyzed threshold ionization (MATI) spectroscopy supported by DFT calculations. The precise ionization energy of Cp*2Mn is determined as 5.349 ± 0.001 eV. The DFT modeling of the MATI spectrum shows that the main structural deformations accompanying the detachment of an electron consist in the elongation of the Mn-C bonds and a change in the Me out-of-plane bending angles. Surprisingly, the DFT calculations predict that most of the reduction in electron density (ED) upon ionization is associated with the hydrogen atoms of the substituents, despite the metal character of the ionized orbital. However, the ED difference isosurfaces reveal a complex mechanism of the charge redistribution involving also the carbon atoms of the molecule.

Electronic states and transitions of PrO and PrO+ probed by threshold ionization spectroscopy and spin-orbit multiconfiguration perturbation theory.

The precise ionization energy of praseodymium oxide (PrO) seeded in supersonic molecular beams is measured with mass-analyzed threshold ionization (MATI) spectroscopy. A total of 33 spin-orbit (SO) states of PrO and 23 SO states of PrO+ are predicted by second-order multiconfigurational quasi-degenerate perturbation (MCQDPT2) theory. Electronic transitions from four low-energy SO levels of the neutral molecule to the ground state of the singly charged cation are identified by combining the MATI spectroscopic measurements with the MCQDPT2 calculations. The precise ionization energy is used to reassess the ionization energies and the reaction enthalpies of the Pr+ O → PrO+ + e- chemi-ionization reaction reported in the literature. An empirical formula that uses atomic electronic parameters is proposed to predict the ionization energies of lanthanide monoxides, and the empirical calculations match well with available precise experimental measurements.

Substitution-induced Nonplanarity of 3-Fluorothioanisole in the First Electronically Excited State.

Vibronic spectra of 3-fluorothioanisole (3FTA) in the first electronic excited state (S1) and the cationic ground state (D0) have been obtained by one-color resonant two-photon ionization (1C-R2PI) and mass-analyzed threshold ionization (MATI) spectroscopy. Spectroscopic measurements and theoretical calculations indicate that both cis- and trans-rotamers of the 3FTA molecule are stable and coexist in the S0 (the electronic ground state) and D0 states, and the cis-rotamer is shown to be slightly more stable than the trans-rotamer. In the S1 state, theoretical calculations predict a stable gauche-structure of 3FTA, manifested by the observation of strong activation of the vibrational modes involving the motion of the -SCH3 group in the low-frequency regions of the 1C-R2PI and MATI spectra. The electronic excitation energy from the S0 state to the S1 state (E1) and the adiabatic ionization energy (IE) are respectively determined to be 34 820 ± 3 and 65 468 ± 5 cm-1 for cis-3FTA, and those of the trans-rotamer are respectively determined to be 35 047 ± 3 and 65 644 ± 5 cm-1. The structural properties of the stable rotamers of 3FTA and their comparison with other F- and Cl-substituted thioanisole derivatives are discussed as well.

Excited states of lutetium oxide and its singly charged cation.

Vibronic spectra of lutetium oxide (LuO) seeded in supersonic molecule beams are investigated with mass-analyzed threshold ionization (MATI) spectroscopy and second-order multiconfigurational quasi-degenerate perturbation (MCQDPT2) theory. Six states of LuO and four states of LuO+ are located by the MCQDPT2 calculations, and an a3Π(LuO+) ← C2Σ+ (LuΟ) transition is observed by the MATI measurement. The vibronic spectra show abnormal vibrational intervals for both the neural and cation excited states, and the abnormality is attributed to vibrational perturbations induced by interactions with neighboring states.

Studies of the First Electronically Excited State of 3-Fluoropyridine and Its Ionic Structure by Means of REMPI, Two-Photon MATI, One-Photon VUV-MATI Spectroscopy and Franck–Condon Analysis

3-Fluoropyridine has been investigated by means of resonance-enhanced multi photon ionization, mass-analyzed threshold ionization (MATI) and one-photon VUV-MATI spectroscopy to study the effect of m-fluorine substitution on the involved states.

Two-color resonance enhanced two-photon ionization and mass analyzed threshold ionization spectroscopy of <i>p</i>-chlorobenzonitrile

The vibrational features of <i>p</i>-chlorobenzonitrile in its first electronically excited state S<sub>1</sub> and cationic ground state D<sub>0</sub> have been investigated by two-color resonance enhanced two-photon ionization and mass analyzed threshold ionization spectroscopy. The excitation energy of S<sub>1</sub> ← S<sub>0</sub> and the ionization energy of <sup>35</sup>Cl and <sup>37</sup>Cl isotopomers of <i>p</i>-chlorobenzonitrile are determined to be 35818 ± 2, and 76846 ± 5 cm<sup>–1</sup>, respectively. These two isotopomers have similar vibrational features. Most of the active vibrations in the S<sub>1</sub> and D<sub>0</sub> states are related to the motions of the in-plane ring deformation. The stable structures and vibrational frequencies of <i>p</i>-chlorobenzonitrile are also calculated by the B3LYP/aug-cc-pVDZ method for the S<sub>0</sub> and D<sub>0</sub> states, and TD-B3LYP/aug-cc-pVDZ method for the S<sub>1</sub> state. The changes in the molecular geometry are discussed in the S<sub>1</sub> ← S<sub>0</sub> photoexcitation process and the D<sub>0</sub> ← S<sub>1</sub> photoionization process. The comparisons between the transition energy of <i>p</i>-chlorophenol, <i>p</i>-chloroaniline, <i>p</i>-chloroanisole, and <i>p</i>-chlorobenzonitrile with those of phenol, anisole, aniline, and benzonitrile provide an insight into the substitution effect of Cl atom.

Development and Verification of Conformer-Specific Vibrational Spectroscopy.

Conformers have similar vibrational structures both in neutral (S0) and cationic (D0) states owing to the comparable force fields between their nuclei. Nevertheless, there is a continuous development of vibrational spectroscopic techniques to rigorously identify individual conformers in the designated molecule but only in the S0 state. We developed an inventive conformer-specific vibrational spectroscopic technique to measure identifiable vibrational spectra of individual conformers in both S0 and D0 states. We measured isomer-specific vibrational spectra in both states for gas-phase acetone and oxetane isomers from a solution with azeotropic composition to verify the proposed techniques that are based on infrared (IR) resonant vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. The measured IR dip VUV-MATI and IR hole-burn VUV-MATI spectra for each isomer, which correspond to isomer-specific vibrational spectra in both states, can be represented by IR-resonant VUV photoionization and one-photon VUV-MATI spectra of the binary mixture, respectively, under supersonic expansion conditions. The partial pressures of the individual isomers in the binary mixture with different mole fractions estimated according to the relative peak intensities in the measured spectra provide insights on solute-solvent interactions. We suggest that the verified IR-resonant VUV-MATI spectroscopy can form the basis of effective schemes toward conformational chemistry.

Vibronic transitions and spin-orbit coupling of three-membered metallacycles formed by lanthanide-mediated dehydrogenation of dimethylamine.

Metal-mediated N-H and C-H bond activation of aliphatic amines is an effective strategy for synthesizing biologically important molecules. Ln (Ln = La and Ce) atom reactions with dimethylamine are carried out in a pulsed-laser vaporization supersonic molecular beam source. A series of dehydrogenation species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln-containing species in the formula Ln(CH2NCH3) are characterized by single-photon mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and multiconfiguration self-consistent field and quasi-degenerate perturbation theory for the Ce species. The MATI spectrum of La(CH2NCH3) consists of a single vibronic band system, which is assigned to the ionization of the doublet ground state of N-methyl-lanthanaaziridine. The MATI spectrum of Ce(CH2NCH3) displays two vibronic band systems, which are attributed to the ionization of two-pair lowest-energy spin-orbit coupling states of N-methyl-ceraaziridine. Both metallaaziridines are three-membered metallacycles and formed by the thermodynamically and kinetically favorable concerted dehydrogenation of the amino group and one of the methyl groups.

Probing the Photoionization Dynamics of 2-Cyclopenten-1-one via High-Resolution VUV-MATI Spectroscopy.

2-Cyclopenten-1-one (2CP), which is a cyclic enone, has been considered an important precursor because of its versatile functionality in the synthesis of natural products and materials for biofuels. Here, we report the adiabatic ionization energy (AIE) and cationic structure of 2CP in the ionic transition between the neutral S0 and the cationic D0 states probed by high-resolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. From the 0-0 band position in the VUV-MATI spectrum supported by the VUV-photoionization efficiency curve, the AIE of 2CP was determined to be 9.3477 ± 0.0004 eV (75,395 ± 3 cm-1), which is in good agreement with the reference value but much more accurate. The measured MATI spectrum combined with the Franck-Condon fitting at the B3LYP/cc-pVTZ level revealed that the cationic structure of 2CP is twisted with the C1 symmetry, whereas the neutral 2CP has the CS symmetry. The results indicate that geometrical changes induced by ionization are mainly attributed to the electron removal from the highest occupied molecular orbital, which consists of nonbonding orbitals on the oxygen atom in the carbonyl group interacting with the σ orbitals in the molecular plane of 2CP. Consequently, lowering the C1 symmetry for cationic 2CP led to the promotions of the ring-bending and ring-twisting modes in the MATI spectrum, which correspond to the ring puckering and C═C twisting in the S0 state, respectively.

Threshold Ionization Spectroscopy and Theoretical Calculations of LnO (Ln = La and Ce).

Mass-analyzed threshold ionization (MATI) spectroscopy was used to measure the vibronic spectra of LnO (Ln = La and Ce). Single-reference coupled cluster and relativistic multireference configuration calculations were carried out to compare with the measured vibronic energies. The spectrum of LaO displays a single vibronic band system, while that of CeO shows multiple ones. The ionization energies of LaO and CeO are measured as 5.2446(6) and 5.3332(6) eV, respectively, which are a 100-fold improvement over the literature values. The vibrational energies of the neutral molecule and corresponding ion reveal the charge effect on the metal-oxygen bond of both species. The single band system in the spectrum of LaO arises from the transition of the ground state of the neutral molecule with the La(6s1)O(2p6) valence configuration to the ground state of the singly charged ion with the La(6s0)O(2p6) configuration. The multiple band systems in the spectrum of CeO are attributed to the spin-orbit coupling for the Ce(4f16s1)O(2p6) configuration of the neutral molecule and an excited state for the Ce(4f1)O(2p6) configuration of the ion.

Identification of individual conformers in C4H6O isomers using conformer-specific vibrational spectroscopy.

We measured the conformer-specific vibrational spectra of C4H6O isomers in neutral and cationic states using IR resonant vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy for the first time. Notably, the measured IR dip and hole-burn VUV-MATI spectra for each isomer represent the identifiable vibrational spectra of individual conformers in both states. Furthermore, we estimated the relative populations of individual conformers in crotonaldehyde (CA) and methyl vinyl ketone (MVK) isomers using the IR dip intensity, the corresponding Franck–Condon factor, and the IR absorption cross section. Our analysis revealed that the compositional ratio of s-trans to s-cis conformers in the CA isomer remained at 95.8 : 4.2 even under supersonic expansion, whereas that in the MVK isomer was determined as 90.6 : 9.4, which is consistent with previous research. These findings reveal that the conformational stability of each isomer depends on the position of the methyl group relative to the carbonyl group.

Laser spectroscopic and computational insights into unexpected structural behaviours of sandwich complexes upon ionization.

Transition-metal sandwich complexes play key roles in various fields such as fundamental and applied chemistry; many of their unique properties arise from their ability to form stable or reactive ions. The first mass-analyzed threshold ionization (MATI) spectra of mixed sandwich compounds, (Ch)(Cp)Cr and (Cot)(Cp)Ti (Ch = η7-C7H7, Cp = η5-C5H5, Cot = η8-C8H8), presented in this work provide an extremely accurate description of the electron detachment. The ionization energies of the neutrals and stabilization energies of the metal-ligand interactions upon ionization are derived from the MATI data with an accuracy of 0.0006 eV. In combination with DFT calculations, laser threshold ionization spectroscopy reveals surprisingly different structural variations accompanying the detachment of the non-bonding dz2 electron from the sandwich molecules. The geometry of (Ch)(Cp)Cr remains practically unchanged while the ionization of (Cot)(Cp)Ti causes a noticeable shortening of the inter-ring distance, similar to that resulting from the ionization of a typical antibonding orbital. Electron density analysis throws light on the nature of these amazing effects.

Conformational structure of cationic tetrahydropyran by one-photon vacuum ultraviolet mass-analyzed threshold ionization spectroscopy.

Isolating and identifying the conformational forms of molecules are imperative processes to investigate the chemical reaction pathways of individual conformers. Herein, we explored the conformational structures of tetrahydropyran in the neutral (S0) and cationic (D0) states by varying the supersonic expansion conditions using one-photon vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. The constructed 2D potential energy surfaces associated with conformational interconversion between the chair and boat forms in the S0 and D0 states revealed that the ionic transitions observed in the MATI spectra correspond to the most stable chair conformer. Accordingly, based on the 0-0 band in the VUV-MATI spectrum supported by the VUV photoionization efficiency curve, the adiabatic ionization energy for the conversion of the chair conformer to a cationic state was determined to be 74 687 ± 4 cm-1 (9.2600 ± 0.0005 eV). Definitive vibrational assignment of the measured MATI spectra using Franck-Condon fitting revealed the cationic structure of the twisted chair conformer. The geometrical change upon ionization promoted the vibrational modes associated with ring inversion and deformation motions in the cationic state. This behavior, which was attributed to the effect of electron removal from the highest occupied molecular orbital (HOMO) consisting of the nonbonding orbital of the oxygen atom, reveals the role of electrons in the HOMO.

Spectroscopic and computational characterization of lanthanide-mediated N–H and C–H bond activation of methylamine

Ln (Ln = La and Ce) atom reactions with methylamine are carried out in a pulsed-laser vaporization supersonic molecular beam source. A series of dehydrogenation species are observed with time-of-flight mass spectrometry, and the dehydrogenated Ln-containing species in the formula Ln(NCH3) are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and density functional theory and multiconfiguration spin-orbit coupling computations. The MATI spectrum of La(NCH3) consists of two vibronic band systems that are assigned to the ionization of the 2A1 ground state of the C3v isomer La(N-CH3) and the 2A' ground state of the Cs isomer La(NH-CH2). The MATI spectrum of Ce(NCH3) also displays two band systems, which are attributed to the ionization of the low-energy spin-orbit coupling states of the C3v isomer Ce(N-CH3). Ln(N-CH3) is formed by the concerted dehydrogenation of the amino group, while La(NH-CH2) is formed by the dehydrogenation of both amino and methyl groups. Ce(NH-CH2) is presumably formed in the reaction based on the computational predictions but not observed by the spectroscopic measurements.

Spin–orbit coupling and vibronic transitions of Ce(C3H4) and Ce(C3H6) formed by the Ce reaction with propene: Mass-analyzed threshold ionization and relativistic quantum computation

A Ce atom reaction with propene is carried out in a pulsed laser vaporization molecule beam source. Several Ce-hydrocarbon species formed by the C-H and C-C bond activation of propene are observed by time-of-flight mass spectrometry, and Ce(C3Hn) (n = 4 and 6) are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and density functional theory, multiconfiguration, and relativistic quantum chemical calculations. The MATI spectrum of each species consists of two vibronic band systems, each with several vibronic bands. Ce(C3H6) is identified as an inserted species with Ce inserting into an allylic C-H bond of propene and Ce(C3H4) as a metallocycle through 1,2-vinylic dehydrogenation. Both species have a Cs structure with the Ce 4f16s1 ground valence electron configuration in the neutral molecule and the Ce 4f1 configuration in the singly charged ion. The two vibronic band systems observed for each species are attributed to the ionization of two pairs of the lowest spin-orbit coupled states with each pair being nearly degenerate.