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1. Efficiency of charge transfer in changing the dissociation dynamics of OD+ transients formed after the photo-fragmentation of D2O

   https://doi.org/10.1063/5.0159300  

   Iskandar, W; Rescigno, T N; Orel, A E; Severt, T; Larsen, K A; Streeter, Z L; Jochim, B; Griffin, B; Call, D; Davis, V; et al (September 2023, The Journal of Chemical Physics)

   We present an investigation of the relaxation dynamics of deuterated water molecules after direct photo-double ionization at 61 eV. We focus on the very rare D+ + O+ + D reaction channel in which the sequential fragmentation mechanisms were found to dominate the dynamics. Aided by theory, the state-selective formation and breakup of the transient OD+(a1Δ, b1Σ+) is traced, and the most likely dissociation path—OD+: a1Δ or b1Σ+ → A 3Π → X 3Σ− → B 3Σ−—involving a combination of spin–orbit and non-adiabatic charge transfer transitions is determined. The multi-step transition probability of this complex transition sequence in the intermediate fragment ion is directly evaluated as a function of the energy of the transient OD+ above its lowest dissociation limit from the measured ratio of the D+ + O+ + D and competing D+ + D+ + O sequential fragmentation channels, which are measured simultaneously. Our coupled-channel time-dependent dynamics calculations reproduce the general trends of these multi-state relative transition rates toward the three-body fragmentation channels. 

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2. Mechanistic molecular motion of transition-metal mediated β-hydrogen transfer: quasiclassical trajectories reveal dynamically ballistic, dynamically unrelaxed, two step, and concerted mechanisms

   https://doi.org/10.1039/D0DT01687J  

   Wheeler, Josh I.; Carlsen, Ryan; Ess, Daniel H. (June 2020, Dalton Transactions)

   null (Ed.)

   The transfer of a β-hydrogen from a metal-alkyl group to ethylene is a fundamental organometallic transformation. Previously proposed mechanisms for this transformation involve either a two-step β-hydrogen elimination and migratory insertion sequence with a metal hydride intermediate or a one-step concerted pathway. Here, we report density functional theory (DFT) quasiclassical direct dynamics trajectories that reveal new dynamical mechanisms for the β-hydrogen transfer of [Cp*Rh III (Et)(ethylene)] + . Despite the DFT energy landscape showing a two-step mechanism with a Rh–H intermediate, quasiclassical trajectories commencing from the β-hydrogen elimination transition state revealed complete dynamical skipping of this intermediate. The skipping occurred either extremely fast (typically <100 femtoseconds (fs)) through a dynamically ballistic mechanism or slower through a dynamically unrelaxed mechanism. Consistent with trajectories begun at the transition state, all trajectories initiated at the Rh–H intermediate show continuation along the reaction coordinate. All of these trajectory outcomes are consistent with the Rh–H intermediate <1 kcal mol −1 stabilized relative to the β-hydrogen elimination and migratory insertion transition states. For Co, which on the energy landscape is a one-step concerted mechanism, trajectories showed extremely fast traversing of the transition-state zone (<50 fs), and this concerted mechanism is dynamically different than the Rh ballistic mechanism. In contrast to Rh, for Ir, in addition to dynamically ballistic and unrelaxed mechanisms, trajectories also stopped at the Ir–H intermediate. This is consistent with an Ir–H intermediate that is stabilized by ∼3 kcal mol −1 relative to the β-hydrogen elimination and migratory insertion transition states. Overall, comparison of Rh to Co and Ir provides understanding of the relationship between the energy surface shape and resulting dynamical mechanisms of an organometallic transformation. 

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3. Mechanisms and dynamics of the NH ⁺ ₂ + H ⁺ and NH ⁺ + H ⁺ + H fragmentation channels upon single-photon double ionization of NH ₃

   https://doi.org/10.1088/1361-6455/abc3aa  

   Larsen, Kirk A; Rescigno, Thomas N; Streeter, Zachary L; Iskandar, Wael; Heck, Saijoscha; Gatton, Averell; Champenois, Elio G; Severt, Travis; Strom, Richard; Jochim, Bethany; et al (November 2020, Journal of Physics B: Atomic, Molecular and Optical Physics)

   Abstract We present state-selective measurements on the N H 2 + + H + and NH + + H + + H dissociation channels following single-photon double ionization at 61.5 eV of neutral NH 3 , where the two photoelectrons and two cations are measured in coincidence using 3D momentum imaging. Three dication electronic states are identified to contribute to the N H 2 + + H + dissociation channel, where the excitation in one of the three states undergoes intersystem crossing prior to dissociation, producing a cold N H 2 + fragment. In contrast, the other two states directly dissociate, producing a ro-vibrationally excited N H 2 + fragment with roughly 1 eV of internal energy. The NH + + H + + H channel is fed by direct dissociation from three intermediate dication states, one of which is shared with the N H 2 + + H + channel. We find evidence of autoionization contributing to each of the double ionization channels. The distributions of the relative emission angle between the two photoelectrons, as well as the relative angle between the recoil axis of the molecular breakup and the polarization vector of the ionizing field, are also presented to provide insight on both the photoionization and photodissociation mechanisms for the different dication states. 

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4. Single-Step Extraction of Transformer Attention with Dual-Gated Memtransistor Crossbars

   https://doi.org/10.1109/LED.2024.3435540  

   Jayasinghe, Nethmi; Hashem, Maeesha Binte; Jayasuriya, Dinithi; Rahimifard, Leila; Kang, Min-A; Sangwan, Vinod K; Hersam, Mark C; Trivedi, Amit Ranjan (October 2024, IEEE Electron Device Letters)

   We discuss how a dual-gated memtransistor crossbar can accelerate the extraction of the Transformer’s attention scores. A memtransistor is a novel two-dimensional material-based device that offers non-volatile programmability and gate tunability. Leveraging these attributes, we demonstrate the extraction of quadratic-order products on a single memtransistor and the single-step extraction of attention scores without inferring intermediate query/key vectors. The query/key-free processing of memtransistor-based attention scoring results in 2.37× lower energy with less than half crossbar cells. 

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5. Photofragment imaging differentiates between one- and two-photon dissociation pathways in MgI⁺

   https://doi.org/10.1063/5.0134668  

   Lockwood, Schuyler P; Metz, Ricardo B (February 2023, The Journal of Chemical Physics)

   The bond strength and photodissociation dynamics of MgI+ are determined by a combination of theory, photodissociation spectroscopy, and photofragment velocity map imaging. From 17 000 to 21 500 cm−1, the photodissociation spectrum of MgI+ is broad and unstructured; photofragment images in this region show perpendicular anisotropy, which is consistent with absorption to the repulsive wall of the (1) Ω = 1 or (2) Ω = 1 states followed by direct dissociation to ground state products Mg+ (2S) + I (2P3/2). Analysis of photofragment images taken at photon energies near the threshold gives a bond dissociation energy D0(Mg+-I) = 203.0 ± 1.8 kJ/mol (2.10 ± 0.02 eV; 17 000 ± 150 cm−1). At photon energies of 33 000–41 000 cm−1, exclusively I+ fragments are formed. Over most of this region, the formation of I+ is not energetically allowed via one-photon absorption from the ground state of MgI+. Images show the observed product is due to resonance enhanced two-photon dissociation. The photodissociation spectrum from 33 000 to 38 500 cm−1 shows vibrational structure, giving an average excited state vibrational spacing of 227 cm−1. This is consistent with absorption to the (3) Ω = 0+ state from ν = 0, 1 of the (1) Ω = 0+ ground state; from the (3) Ω = 0+ state, absorption of a second photon results in dissociation to Mg* (3P°J) + I+ (3PJ). From 38 500 to 41 000 cm−1, the spectrum is broad and unstructured. We attribute this region of the spectrum to one-photon dissociation of vibrationally hot MgI+ at low energy and ground state MgI+ at higher energy to form Mg (1S) + I+ (3PJ) products. 

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