First-principles simulations of transition state spectra of the I + HI and I + DI reactions and vibrational bonding in IMuI

Yoshida, T.; Sato, Kazuma; Takayanagi, Toshiyuki

doi:10.1016/j.chemphys.2015.05.019

Cited by 7 publications

(4 citation statements)

References 48 publications

(87 reference statements)

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“…Currently,t he vibrational bonding in three atom species is aw ell-established phenomenon but there are also other more complex systems in which upon replacing ap rotonw ith a m + transition-state-like structures are stabilized. [78][79][80][81][82] Although in all these examples as well as in what is considered in this report one is facedw ith the same type of isotope substitution, the detailed mechanism of bonding and stabilization of transition-state-like structuresa re distinct in each case and different from the vibrational bonding. The identification and classificationofv arioustypes of structural variations resulting from replacing ap roton with a m + is an open problem that needs further considerations.…”

Section: Discussionmentioning

confidence: 79%

“…Although the mainstream view in the chemical community usually assumes that the nuclear mass and its variation are unimportant from structural and bonding viewpoints, the present study and some other recent studies demonstrate that upon sufficiently large mass variations, “chemically” interesting alternations are observable. Currently, the vibrational bonding in three atom species is a well‐established phenomenon but there are also other more complex systems in which upon replacing a proton with a μ + transition‐state‐like structures are stabilized . Although in all these examples as well as in what is considered in this report one is faced with the same type of isotope substitution, the detailed mechanism of bonding and stabilization of transition‐state‐like structures are distinct in each case and different from the vibrational bonding.…”

Section: Discussionmentioning

confidence: 89%

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Muon‐Substituted Malonaldehyde: Transforming a Transition State into a Stable Structure by Isotope Substitution

Goli

Shahbazian

2016

Chemistry A European J

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Isotopes ubstitutionsa re usually conceived to play am arginal role on the structure and bondingp attern of molecules. However,arecent study [Angew.C hem. Int. Ed. 2014, 53,1 3706-13709; Angew.C hem. 2014, 126,1 3925-13929]f urther demonstrates that upon replacing ap roton with ap ositively charged muon, as the lightest radioisotope of hydrogen, radical changes in the nature of the structure and bonding of certains peciesm ay take place. The present report is ap rimary attemptt oi ntroduce another example of structural transformation on the basis of the malonaldehyde system.A ccordingly,u pon replacing the protonb etween the two oxygen atoms of malonaldehydew ith the positively charged muon as erious structuralt ransformationi so bserved. By using the ab initio nuclear-electronic orbitaln onBorn-Oppenheimer procedure, the nuclear configuration of the muon-substituted speciesi sd erived. The resulting nuclear configuration is much more similart ot he transition state of the proton transferi nm alonaldehyde rather than to the stable configuration of malonaldehyde. The comparison of the "atoms in molecules" (AIM) structureoft he muon-substituted malonaldehyde and the AIM structureo ft he stable and the transition-state configurations of malonaldehyde also unequivocally demonstrates substantial similarities of the muon-substituted malonaldehydet ot he transition state.

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Section: Discussionmentioning

confidence: 79%

Section: Discussionmentioning

confidence: 89%

Muon‐Substituted Malonaldehyde: Transforming a Transition State into a Stable Structure by Isotope Substitution

Goli

Shahbazian

2016

Chemistry A European J

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“…This TS is of particular interest, since fluorine atoms often show distinctly different intermolecular interactions, compared to other halogen atoms. For example, the TSs for F • + H 2 → FH + H • and F • + H–Cl → F–H + Cl • , possess bent structures; but, in contrast, the NIPE spectra have been successfully modeled with linear TSs in studies of the heavier halogen analogs in X • + H–Y → X–H + Y • reactions (X, Y ≠ F). ,− The TS for F • + H–F → F–H + F • has also been predicted to be bent …”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Studies of the F^• + H–F Transition-State Region by Photodetachment of [F–H–F]⁻

et al. 2017

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The transition-state (TS) region of the simplest heavy-light-heavy type of reaction, F + H-F → F-H + F, is investigated in this work by a joint experimental and theoretical approach. Photodetaching the bifluoride anion, [F···H···F], generates a negative ion photoelectron (NIPE) spectrum with three partially resolved bands in the electron binding energy (eBE) range of 5.4-7.0 eV. These bands correspond to the transition from the ground state of the anion to the electronic ground state of [F-H-F] neutral, with associated vibrational excitations. The significant increase of eBE of the bifluoride anion, relative to that of F, reflects a hydrogen bond energy between F and HF of ∼46 kcal/mol. Theoretical modeling reveals that the antisymmetric motion of H between the two F atoms, near the TS on the neutral [F-H-F] surface, dominates the observed three bands, while the F-H-F bending, F-F symmetric stretching modes, and the couplings between them are calculated to account for the breadth of the observed spectrum. From the NIPE spectrum, a lower limit on the activation enthalpy for F + H-F → F-H + F can be estimated to be ΔH = 12 ± 2 kcal/mol, a value below that of ΔH = 14.9 kcal/mol, given by our G4 calculations.

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“…[1][2][3][4][5][6] A very interesting aspect of muonium, Mu, chemistry, recently highlighted in the literature, is the possibility of inducing a fundamental change in the nature of chemical bonding by Mu isotopic substitution. [7][8][9][10][11][12][13][14][15] Specifically, rigorous QM calculations have shown that the ''heavy-light-heavy'' system BrLBr, where L is an isotope of hydrogen, can change from van der Waals to vibrational bonding when L = Mu. 8 In contrast to conventional chemical bonding, that is due to a minimum in the potential energy, often associated with a slight increase in ZPE, vibrational bonding results from a decrease in ZPE in a minimum-free potential energy surface (PES).…”

Section: Introductionmentioning

confidence: 99%

Influence of vibration in the reactive scattering of D + MuH: the effect of dynamical bonding

Sáez-Rábanos

Verdasco

Aoiz

et al. 2016

Phys. Chem. Chem. Phys.

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The dynamics of the D+MuH(υ=1) reaction has been investigated using time-independent quantum mechanical calculations. Total reaction cross sections and rate coefficients have been calculated for the two exit channels of the reaction leading respectively to DMu+H and DH+Mu. Over the 100-1000K temperature range investigated the rate coefficients for the DMu+H channel are of the order of 10 −10 cm 3 s −1 and those for the DH+Mu channel vary between 1·10 −12 −8·10 −11 cm 3 s −1 . These results point to a virtually barrierless reaction for the DMu+H channel and to the presence of a comparatively small barrier for the DH+Mu channel and are consistent with the profiles of their respective collinear vibrationally adiabatic potentials (VAPs). The effective barrier in the VAP of the DH+Mu channel is located in the reactants valley and, consequently, translation is found to be more efficient than vibration for the promotion of the reaction over a large energy interval in the post threshold region. Below this barrier, the DH+Mu channel can be accessible through an indirect mechanism implying a crossing from the DMu+H pathway.The most salient feature found in the present study is revealed in the total reaction cross section for the DMu+H channel, which shows a sharp resonance caused by the presence of a deep well in the vibrationally adiabatic potential. This well has a dynamical origin, reminiscent of that found recently in the vibrationally bonded BrMuBr complex [Fleming et al. Angew. Chem. Int. Ed. 53, 1, 2014], and is due to the stabilizing effect of the light Mu atom oscillating between the heavier H and D isotopes and to the bond softening associated with vibrational excitation of MuH.

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First-principles simulations of transition state spectra of the I + HI and I + DI reactions and vibrational bonding in IMuI

Cited by 7 publications

References 48 publications

Muon‐Substituted Malonaldehyde: Transforming a Transition State into a Stable Structure by Isotope Substitution

Muon‐Substituted Malonaldehyde: Transforming a Transition State into a Stable Structure by Isotope Substitution

Experimental and Theoretical Studies of the F^• + H–F Transition-State Region by Photodetachment of [F–H–F]⁻

Influence of vibration in the reactive scattering of D + MuH: the effect of dynamical bonding

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First-principles simulations of transition state spectra of the I + HI and I + DI reactions and vibrational bonding in IMuI

Cited by 7 publications

References 48 publications

Muon‐Substituted Malonaldehyde: Transforming a Transition State into a Stable Structure by Isotope Substitution

Muon‐Substituted Malonaldehyde: Transforming a Transition State into a Stable Structure by Isotope Substitution

Experimental and Theoretical Studies of the F• + H–F Transition-State Region by Photodetachment of [F–H–F]−

Influence of vibration in the reactive scattering of D + MuH: the effect of dynamical bonding

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Experimental and Theoretical Studies of the F^• + H–F Transition-State Region by Photodetachment of [F–H–F]⁻