Potential Energy Surfaces for Reactions of X Metal Atoms (X = Cu, Zn, Cd, Ga, Al, Au, or Hg) with  YH<sub>4</sub> Molecules (Y = C, Si, or Ge) and Transition Probabilities at Avoided Crossings in Some Cases

Novaro, O.; Pacheco-Blas, María del Alba; Pacheco-Sánchez, J. H.

doi:10.1155/2012/720197

Cited by 7 publications

(3 citation statements)

References 87 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We fitted the obtained rate constants (see Figure b) according to the Landau–Zener-type formula − k A B ( g ) = k A B 0 ( 1 − e − z g 2 ) where k AB 0 is the lower state transition rate constant and z is a fitting parameter. This expression approximately describes the dependence of the reaction rate constant on the gap size .…”

Section: Resultsmentioning

confidence: 99%

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Reiner

Bachmair

Tiefenbacher

et al. 2023

J. Chem. Theory Comput.

View full text Add to dashboard Cite

We present a rare event sampling scheme applicable to coupled electronic excited states. In particular, we extend the forward flux sampling (FFS) method for rare event sampling to a nonadiabatic version (NAFFS) that uses the trajectory surface hopping (TSH) method for nonadiabatic dynamics. NAFFS is applied to two dynamically relevant excited-state models that feature an avoided crossing and a conical intersection with tunable parameters. We investigate how nonadiabatic couplings, temperature, and reaction barriers affect transition rate constants in regimes that cannot be otherwise obtained with plain, traditional TSH. The comparison with reference brute-force TSH simulations for limiting cases of rareness shows that NAFFS can be several orders of magnitude cheaper than conventional TSH and thus represents a conceptually novel tool to extend excited-state dynamics to time scales that are able to capture rare nonadiabatic events.

show abstract

Section: Resultsmentioning

confidence: 99%

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Reiner

Bachmair

Tiefenbacher

et al. 2023

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…In the past several decades, d-block transition metals have been widely used to catalyze hydrocarbon reactions. − The catalytic behavior of transition metals is highly sensitive to their electron configurations, oxidation states, and surface absorptivity . Among these factors, the electron configuration of the metal atom plays a central role in the C–C and C–H bond activation. − This is because the metal–ligand reactions involve favorable metal–ligand orbital interactions and electron transfer that minimize the activation barrier of C–C and C–H bond dissociation. ,, An effective way for manipulating electronic configurations of the metal atom is by selectively exciting the metal atom to an excited state and then carrying out an excited-state metal–ligand reaction.…”

Section: Introductionmentioning

confidence: 99%

Probing La and Ce Excited-State Reactivity with Resonant Two-Photon Ionization Spectroscopy

2022

View full text Add to dashboard Cite

Dehydrogenation and C−C bond cleavage of 1-butyne by the excited states of La and Ce atoms are investigated in laser-ablation metal molecular beams. The excited states of the metal atoms are prepared by resonant excitation, detected by resonant two-photon ionization spectroscopy, and the reaction products are monitored by photoionization time-of-flight mass spectrometry. The reactivities of La* [5d 2 ( 3 F)6p ( 4 G 5/2 °)] and Ce* [4f5d( 3 F°)6s6p( 3 P°) ( 5 H 5 )]excited states are observed to be higher than those of the initial states of the corresponding metal atoms. The higher reactivities of the excited states are attributed to their higher energies and favorable electron configurations to form two covalent bonds of the metal-insertion intermediates. Although both excited La and Ce atoms show increased reactivities, the enhancement for Ce is much more pronounced than that of La, which cannot be explained by electron configurations alone. The larger reactivity enhancement from the initial states to the excited state of the Ce atom than that of La is due to the longer lifetime of the Ce excited state.

show abstract

“…By using the pump–probe technique, Breckenridge and co-workers have thoroughly investigated the reactions of n s n p metal atoms with H 2 , CH 4 , SiH 4 , and GeH 4 in the gas phase . The experimental and theoretical studies suggest that the reactions of the n s n p ( 1 P) excited-state group II metal atoms with EH 4 (E = C, Si, Ge) molecules favored the side-on insertion mechanism instead of direct abstraction of H from EH 4 by end-on attack of the E–H bond. − The reactions of methane with naked metal atoms have been widely studied using the matrix isolation technique. In the low-temperature noble gas matrix, laser-ablated group IIA (Be, Mg, and Ca) and group IIB (Zn, Cd, and Hg) metal atoms react with methane upon photolysis, leading to the formation of HMCH 3 molecules.…”

Section: Introductionmentioning

confidence: 99%

Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)₃E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies

Zhao

Xiao

et al. 2020

Inorg. Chem.

View full text Add to dashboard Cite

Matrix isolation infrared spectroscopy combined with quantumchemical calculations were employed to study the reactions of calcium atoms with silane, germane, and stannane in a 4 K argon matrix. The ion pairs [HCa] + and [EH 3 ] − (E = Si, Ge, and Sn) in both the classical structure HCaEH 3 and the bridged structure HCa(μ-H) 3 E were identified based on the H/D isotopic substitution experiments and quantum-chemical calculations. The results show that the reaction between ground-state Ca and EH 4 proceeds inefficiently, and only after the photolytic activation of Ca atoms to the Ca( 1 P:4s4p) state does insertion occur to give HCaEH 3 , which rearranges to HCa(μ-H) 3 E upon photolysis. Topological analysis of the electronic structure suggests that the nonclassical structure HCa(μ-H) 3 E is formed by the electrostatic interaction with charge-inverted hydrogen bridge bond, while HCaEH 3 is dominated by (HCa) + (EH 3 ) − ion pair interactions.

show abstract

Potential Energy Surfaces for Reactions of X Metal Atoms (X = Cu, Zn, Cd, Ga, Al, Au, or Hg) with YH₄ Molecules (Y = C, Si, or Ge) and Transition Probabilities at Avoided Crossings in Some Cases

Abstract: Review: ab initio studies based on quantum mechanics; 104 refs.

Cited by 7 publications

References 87 publications

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Probing La and Ce Excited-State Reactivity with Resonant Two-Photon Ionization Spectroscopy

Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)₃E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies

Contact Info

Product

Resources

About

Potential Energy Surfaces for Reactions of X Metal Atoms (X = Cu, Zn, Cd, Ga, Al, Au, or Hg) with YH4 Molecules (Y = C, Si, or Ge) and Transition Probabilities at Avoided Crossings in Some Cases

Abstract: Review: ab initio studies based on quantum mechanics; 104 refs.

Cited by 7 publications

References 87 publications

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Probing La and Ce Excited-State Reactivity with Resonant Two-Photon Ionization Spectroscopy

Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)3E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies

Contact Info

Product

Resources

About

Potential Energy Surfaces for Reactions of X Metal Atoms (X = Cu, Zn, Cd, Ga, Al, Au, or Hg) with YH₄ Molecules (Y = C, Si, or Ge) and Transition Probabilities at Avoided Crossings in Some Cases

Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)₃E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies