Search

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. [ABSTRACT FROM AUTHOR]

In the present work, we report exploitation of spatial symmetry in calculations of ground state energy and analytic first derivatives of closed-shell molecules based on our previously developed coupled-cluster (CC) approach with spin-orbit coupling. Both time-reversal symmetry and spatial symmetry for D2h and its subgroups are exploited in the implementation. The symmetry of a certain spin case for the amplitude, intermediate, or density matrix is determined by the symmetry of the corresponding spin functions and the direct product decomposition method is employed in computations involving these quantities. The reduction in computational effort achieved through the use of spatial symmetry is larger than the order of the molecular single point group. Symmetry exploitation renders application of the CC approaches with spin-orbit coupling to larger closed-shell molecules containing heavy elements with high accuracy. [ABSTRACT FROM AUTHOR]

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 Pr atoms is on the order of hundreds of wavenumbers. [ABSTRACT FROM AUTHOR]

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. [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]

Ce atom reactions with ethylene, 2-butene, and isobutene are carried out in a pulsed laser vaporization molecule beam source. Ce-containing species are observed with time-of-flight mass spectrometry, and Ce(C4H6) is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and relativistic quantum chemical calculations. Two structural isomers are identified for Ce(C4H6): one is the tetrahedronlike Ce[C(CH2)3] in C3v symmetry and the other is the five-membered metallocyclic Ce(CH2CHCHCH2) in Cs. The MATI spectrum of the C3v isomer exhibits two vibronic band systems separated by 88 cm−1, while that of the Cs isomer displays three split by 60 and 101 cm−1. The multiple band systems are attributed to spin-orbit splitting and vibronic transitions involving metal-hydrocarbon and hydrocarbon-based vibrations. The splitting in the C3v isomer arises from interactions of two triplet and two singlet states at the lowest energies, while each splitting in the Cs isomer involves two triplets and a singlet. Although the Ce atom has ground electron configuration 4f15d16s2, Ce valence electron configurations in both isomers are 4f16s1 in the neutral ground state and 4f1 in the ion. The remaining Ce 5d electrons in the isolated atom are spin paired in molecular orbitals that are a bonding combination between Ce 5dπ and hydrocarbon π* orbitals. [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]

The rapid progress in the field of organic–inorganic halide perovskite (OIHP) has led to not only >24% power conversion efficiency for photovoltaics, but also provided breakthroughs in processing of materials with tailored functional behavior. This ability to design and synthesize engineered OIHP materials has opened the possibility to develop various other optoelectronic applications. In addition to that of photovoltaics, this includes photodetector, laser, light emitting diode, X-ray and gamma detector, photocatalyst, memory, transducer, transistor, and more. At this stage, the emphasis is on fundamental understanding of the underlying physics and chemistry of OIHP materials, which will assist the evaluation of device performance and provide explanations for some of the contradictory results reported in literature. This review discusses the theoretical and experimental analysis of the OIHP materials reported from various sources and considers the chemical and structural origin of their unique optoelectronic properties, correlated microstructures, and newly discovered extraordinary properties. In the first few sections, we summarize and discuss the crystallography, chemical bonding, and substitutional effects, followed by the discussion of correlated photophysics including the optical, electronic, excitonic, charge transport, and ion migration characteristics. Next, we revisit and discuss the in-depth behavior of films with unique defect structure, structural disorder, morphology, and crystallization thermodynamics. Novel thermal-electrical-optical properties including ferroelectricity, hot-carrier contribution, spin-orbit coupling effect, terahertz time response, edge-state discovery, etc., are rationalized considering the results debated in the community. We elaborate on the opportunities and challenges regarding stability, toxicity, and hysteresis. The viewpoint on commercialization of OIHP based solar module is presented with the goal of identifying near-term opportunities. Throughout this review, the overarching goal is to provide a simplified explanation for the complex physical effects and mechanisms, underlying interconnections between different mechanisms, uncertainties reported in literature, and recent important theoretical and experimental discoveries. [ABSTRACT FROM AUTHOR]

Lanthanum dimer (La2) was studied by mass-analyzed threshold ionization (MATI) spectroscopy and a series of multi-configuration ab initio calculations. The MATI spectrum exhibits three band systems originating from ionization of the neutral ground electronic state, and each system shows vibrational frequencies of the neutral molecule and singly charged cation. The three ionization processes are La2+ (a2∑g+) ← La2 (X1∑g+), La2+ (b2Π3/2, u) ← La2 (X1∑g+), and La2+ (b2Π1/2, u) ← La2 (X1∑g+), with the ionization energies of 39 046, 40 314, and 40 864 cm-1, respectively. The vibrational frequency of the X1Σg+ state is 207 cm-1, and those of the a2Σg+, b2Π3/2, u and b2Π1/2, u are 235.7, 242.2, and 240 cm-1. While X1Σg+ is the ground state of the neutral molecule, a2Σg+ and b2Πu are calculated to be the excited states of the cation. The spin-orbit splitting in the b2Πu ion is 550 cm-1. An X4Σg- state of La2+ was predicted by theory, but not observed by the experiment. The determination of a singlet ground state of La2 shows that lanthanum behaves differently from scandium and yttrium. [ABSTRACT FROM AUTHOR]

Spin transfer torques allow the electrical manipulation of magnetization at room temperature, which is desirable in spintronic devices such as spin transfer torque memories. When combined with spin-orbit coupling, they give rise to spin-orbit torques, which are a more powerful tool for controlling magnetization and can enrich device functionalities. The engineering of spin-orbit torques, based mostly on the spin Hall effect, is being intensely pursued. Here, we report that the oxidation of spin-orbit-torque devices triggers a new mechanism of spin-orbit torque, which is about two times stronger than that based on the spin Hall effect. We thus introduce a way to engineer spin-orbit torques via oxygen manipulation. Combined with electrical gating of the oxygen level, our findings may also pave the way towards reconfigurable logic devices. [ABSTRACT FROM AUTHOR]

The local electronic and crystal structures of self-doped Pr 1- x MnO 3+δ (x = 0.0 and 0.2) perovskites are studied by x-ray absorption spectroscopy at Mn K -, Mn L - and O K -edges. The Mn K -edge shifts towards higher energy with increasing x indicating the increase in average manganese valence, which, in turn, leads to an increase in magnetization. The Mn L -edge spectra display a splitting into L 3 (2 p 3/2) and L 2 (2 p 1/2) peaks which is caused by core hole spin-orbit coupling. The intensities of 2 p 3/2 and 2 p 1/2 peaks increase with x, which correlates with the increase in magnetization and results from the change in hybridization between O 2 p and Mn 3 d orbitals. Altering x do not affect the O K -pre-edge spectra indicating no changes in Fermi level. Difference in relation of magnetic properties to electron structure in self-doped manganites and oxides doped in A - and B -positions of perovskites AB O 3 cell is underlined. The Fourier transform of EXAFS spectra shows the decrease in oxygen and praseodymium contents and the formation of trivalent manganese anti-site defects in praseodymium position with increasing x. [Display omitted] • Local crystal and electron structures of self-doped Pr 1- x MnO 3+δ are studied. • Increase of average manganese valence with increasing x is observed. • Anti-site defects formed by trivalent manganese are observed. • Hybridization of O 2 p and Mn 3 d states correlates with x and magnetization. • Fermi level is almost the same for the perovskites. [ABSTRACT FROM AUTHOR]