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Metal-pyridine (metal=Li, Ca, and Sc) complexes are produced inlaser-vaporization molecular beams and studied by pulsed-field-ionization zero-electron-kinetic-energy (ZEKE) spectroscopy and theoretical calculations. Both σ and π structures are considered for the three complexes by theory, and preferred structures are determined by the combination of the ZEKE spectra and calculations. The Li and Ca complexes prefer a σ bonding mode, whereas the Sc complex favors a π mode. Adiabatic ionization energies and metal-ligand vibrational frequencies are determined from the ZEKE spectra. Metal-ligand bond dissociation energies of the neutral complexes are obtained from a thermodynamic cycle. The ionization energies follow the trend of Li-pyridine (32 460 cm-1)≤Ca-pyridine(39 043 cm-1)≤Sc-pyridine(42 816 cm-1), whereas the bond energies are in the order of Ca-pyridine (27.0 kJ mol-1)≤Li-pyridine(49.1 kJ mol-1)≤Sc-pyridine(110.6 kJ mol-1). The different bonding modes between the main group metals and transition element are discussed in terms of Sc 3d orbital involvement. The bond energy differences between the Li and Ca metals are explained by the number of valence s electrons and the size of the metal atoms. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Group 6 metal–bis(mesitylene)sandwich complexes are produced by interactions between the laser-vaporizedmetal atoms and mesitylene vapor in a pulsed molecular beam source,identified by photoionization time-of-flight mass spectrometry, andstudied by pulsed-field ionization zero-electron kinetic energy spectroscopyand density functional theory calculations. Although transition metal–bis(arene)sandwich complexes may adopt eclipsed and staggered conformations,the group 6 metal–bis(mesitylene) complexes are determinedto be in the eclipsed form. In this form, rotational conformers withmethyl group dihedral angles of 0 and 60° are identified forthe Cr complex, whereas the 0° rotamer is observed for the Moand W species. The 0° rotamer is in a C2vsymmetry with the neutral ground stateof 1A1and the singly positive charged ion stateof 2A1. The 60° rotamer is in a Cisymmetry with the neutralground state of 1Agand the ion state of 2Ag. Partial conversion of the 60 to 0° rotameris observed from He to He/Ar supersonic expansion for Cr–bis(mesitylene).The unsuccessful observation of the 60° rotamer for the Mo andW complexes is the result of its complete conversion to the 0°rotamer in both He and He/Ar expansions. The adiabatic ionizationenergies of the 0° rotamers of the three complexes are in theorder of Cr–bis(mesitylene) < W–bis(mesitylene)

La atom reaction with isoprene is carried out in a laser-vaporization molecular beam source. The reaction yields an adduct as the major product and C—C cleaved and dehydrogenated species as the minor ones. La(C5H8), La(C2H2), and La(C3H4) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of all three species exhibit a strong origin band and several weak vibronic bands corresponding to La-ligand stretch and ligand-based bend excitations. La(C5H8) is a five-membered metallacycle, whereas La(C2H2) and La(C3H4) are three-membered rings. All three metallacycles prefer a doublet ground state with a La 6s1-based valence electron configuration and a singlet ion. The five-membered metallacycle is formed through La addition and isoprene isomerization, whereas the two three-membered rings are produced by La addition and insertion, hydrogen migration, and carbon-carbon bond cleavage. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C4H6) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C4H6) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these spectra shows a strong origin band and several vibrational progressions. The two band systems from the spectrum of the 1-butene reaction are assigned to the ionization of two isomers: La[C(CH2)3] (Iso A) and La(CH2CHCHCH2) (Iso B), and the single band system from the spectra of the 2-butene and isobutene reactions is attributed to Iso B and Iso A, respectively. The ground electronic states are 2A1 (C3v) for Iso A and 2A′ (Cs) for Iso B. The ionization of the doublet state of each isomer removes a La 6s-based electron and leads to the 1A1 ion of Iso A and the 1A′ ion of Iso B. The formation of both isomers consists of La addition to the C=C double bond, La insertion into two C(sp3)—H bonds, and H2 elimination. In addition to these steps, the formation of Iso A from the La+1-butene reaction may involve the isomerization of 1-butene to isobutene prior to the C—H bond activation, whereas the formation of Iso B from the La+trans-2-butene reaction may include the trans- to cis-butene isomerization after the C—H bond activation. [ABSTRACT FROM AUTHOR]

Copper complexes of 2,2′-bipyridine (22BIPY) and 4,4′-bipyridine (44BIPY) were prepared in a laser-vaporization supersonic molecular beam source and identified by laser photoionization time-of-flight mass spectrometry. Electronic spectra and molecular structures were studied with pulsed-field ionization zero electron kinetic energy (ZEKE) electron spectroscopy, density functional theory (DFT) and second-order Møller-Plesset perturbation (MP2) calculations, and spectral simulations. Adiabatic ionization energies and metal-ligand and ligand-based vibrational frequencies of Cu-22BIPY and Cu-44BIPY were measured from the ZEKE spectra. Ground electronic states and molecular structures of the two complexes were determined by comparing the spectroscopic measurements with the theoretical calculations. The ground state of Cu-22BIPY (2B1, C2 v) has a planar bidentate structure with Cu binding to two nitrogen atoms and two pyridine molecules in the cis configuration. The ground state of Cu-44BIPY (2A, C2) has a monodentate structure with Cu binding to one nitrogen and two pyridines in a twisted configuration. The ionization energy of Cu-22BIPY is considerably lower and its bond energy is much higher than that of Cu-44BIPY. The different ionization and dissociation energies are attributed to the distinct metal binding modes of the two complexes. It has been found that the DFT calculations yield the correct structures for the Cu-22BIPY complex, whereas the MP2 calculations produce the best structures for the Cu-44BIPY complex. [ABSTRACT FROM AUTHOR]

M3O4 (M = Sc, Y, and La) were produced in a pulsed laser-vaporization molecular beam source and studied by mass-analyzed threshold ionization (MATI) spectroscopy and electronic structure calculations. Adiabatic ionization energies (AIEs) of the neutral clusters and vibrational frequencies of the cations were measured accurately for the first time from the MATI spectra. Five possible structural isomers of M3O4 were considered in the calculations and spectral analysis. A cage-like structure in C3v point group was identified as the most stable one. The structure is formed by fusing three M2O2 fragments together, each sharing two O-M bonds with others. The ground electronic state of the neutral clusters is 2A1 with the unpaired electron being largely a metal-based s character. Ionization of the 2A1 state yields a 1A1 ion state in a similar geometry to the neutral cluster. The AIEs of the clusters are 4.4556 (6), 4.0586(6), and 3.4750(6) eV for M = Sc, Y, and La, respectively. The observed vibrational modes of the cations include metal-oxygen stretching, metal triangle breathing, and oxygen-metal-oxygen rocking in the frequency range of 200-800 cm-1. [ABSTRACT FROM AUTHOR]

Neodymium (Nd) complexes of benzene and naphthalene were synthesized in a laser-ablation supersonic molecular beam source. High-resolution electron spectra of these complexes were obtained using pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy. Second-order Mo\ller-Plesset perturbation calculations were employed to aid spectral and electronic-state assignments. The adiabatic ionization energies were measured to be 38 081 (5) cm-1 for Nd(benzene) and 37 815 (5) cm-1 for Nd(naphthalene). For the Nd(benzene) complex, the observed frequencies of 831 and 286 cm-1 were assigned to C-H out-of-plane bending and Nd+-C6H6 stretching modes in the 6A1 ion state and 256 cm-1 to the Nd-C6H6 stretching mode in the 7A1 neutral state. To confirm these assignments, the ZEKE spectrum of the deuterated species was recorded, and the corresponding vibrational frequencies were measured to be 710 and 277 cm-1 in the ion state and 236 cm-1 in the neutral state. For the Nd(naphthalene) complex, the observed vibrational modes were C10H8 bending (394 cm-1), Nd+-C10H8 stretching (286 and 271 cm-1), Nd+-C10H8 bending (80 cm-1), and C10H8 twisting (105 cm-1) in the 6A′ ion state and metal-ligand bending (60 cm-1) and ligand twisting (55 cm-1) in the 7A′ neutral state. The formation of the ground state of the Nd(benzene) complex requires 4f → 5d and 6s → 5d electron excitation of the Nd atom, whereas the formation of the ground state of Nd(naphthalene) involves the 6s → 5d electron promotion. [ABSTRACT FROM AUTHOR]

Al-thymine (Al–C4H3N2O2CH3) is produced by laser vaporization of a rod made of Al and thymine powders in a molecular beam and studied by single-photon pulsed-field ionization-zero electron kinetic energy (ZEKE) photoelectron and IR-UV resonant two-photon ionization spectroscopy and density functional theory calculations. The ZEKE experiment determines the adiabatic ionization energy of the neutral complex and 22 vibrational modes for the corresponding ion with frequencies below 2000 cm-1. The IR-UV photoionization experiment measures two N–H and three C–H stretches for the neutral species. The theoretical calculations predict a number of low-energy isomers with Al binding to single oxygen or adjacent oxygen and nitrogen atoms of thymine. Among these isomers, the structure with Al binding to the O4 atom of the diketo tautomer is predicted to be the most stable one by the theory and is probed by both ZEKE and IR-UV measurements. This work presents the first application of the IR-UV resonant ionization to metal-organic molecule systems. Like ZEKE spectroscopy, the IR-UV photoionization technique is sensitive for identifying isomeric structures of metal association complexes. [ABSTRACT FROM AUTHOR]

The gallium complexes were produced in pulsed molecular beams and studied with zero electron kinetic energy (ZEKE) photoelectron spectroscopy. Intermolecular vibrational frequencies and adiabatic ionization potentials (IPs) were obtained from ZEKE spectra. Ground electronic states were identified by combining the ZEKE spectra with quantum chemical and Franck–Condon calculations. Ga–NH[sub 3] has an IP of 40 135 cm-1 and metal-ligand stretching frequencies of 270 cm-1 (ω[sub s][sup +]) in the ion and 161 cm-1 (ν[sub s]) in the neutral. The IP of Ga–NH[sub 2]CH[sub 3] is 39 330 cm-1, and the vibrational frequencies are 93 cm-1 (ν[sub b]) for the Ga–N–C bending, 124 cm-1 (ω[sub b][sup +]) for the Ga[sup +]–N–C bending, and 299 cm-1 (ω[sub s][sup +]) for the Ga[sup +]–N stretching. The strength of the gallium–methylamine binding is stronger than that of the gallium–ammonia. The ground state of Ga–NH[sub 3] is [sup 2]A[sup ′](C[sub s]) and that of Ga[sup +]–NH[sub 3] is [sup 1]A[sub 1](C[sub 3v]). In contrast, Ga–NH[sub 2]CH[sub 3] has two doublets, [sup 2]A[sup ′] and [sup 2]A[sup ″](C[sub s]), with virtually the same energies, whereas Ga[sup +]–NH[sub 2]CH[sub 3] has a [sup 1]A[sup ′](C[sub s]) ground state. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Threshold photoionization and pulsed-field-ionization zero-electron-kinetic-energy photoelectron spectra have been used to study the vibrational cooling of Cu–N(CH3)3 and the electronic cooling of Al–NH3 in helium and argon supersonic jets. The vibrational temperatures of Cu–N(CH3)3 are estimated to be ∼40 K in argon and ∼120 K in helium, whereas the electronic temperatures of Al–NH3 are about 20 and 80 K, respectively. Argon more efficiently cools the internal degrees of freedom of the metal systems, but helium provides additional spectroscopic information about the neutral molecules. The differences in the observed spectra have greatly facilitated spectral assignments for these complexes. [Copyright &y& Elsevier]

Monobenzene complexes of yttrium (Y), lanthanum (La), and lutetium (Lu), M(C6H6) (M = Y, La, and Lu), were prepared in a laser-vaporization supersonic molecular beam source and studied by pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy and ab initio calculations. The calculations included the second-order perturbation, the coupled cluster with single, double, and perturbative triple excitation, and the complete active space self-consistent field methods. Adiabatic ionization energies and metal-benzene stretching frequencies of these complexes were measured for the first time from the ZEKE spectra. Electronic states of the neutral and ion complexes and benzene ring deformation were determined by combining the spectroscopic measurements with the theoretical calculations. The ionization energies of M(C6H6) are 5.0908 (6), 4.5651 (6), and 5.5106 (6) eV, and the metal-ligand stretching frequencies of [M(C6H6)]+ are 328, 295, and 270 cm-1 for M = Y, La, and Lu, respectively. The ground states of M(C6H6) and [M(C6H6)]+ are 2A1 and 1A1, respectively, and their molecular structures are in C2v point group with a bent benzene ring. The deformation of the benzene ring upon metal coordination is caused by the pseudo Jahn-Teller interaction of (12E2+12A1+22E2) x e2 at C6v symmetry. In addition, the study shows that spectroscopic behaviors of Y(C6H6) and La(C6H6) are similar to each other, but different from that of Lu(C6H6). [ABSTRACT FROM AUTHOR]