Threshold photoelectron spectroscopy of iminoborane, HBNH

Schleier, Domenik; Schaffner, Dorothee; Gerlach, Marius; Hemberger, Patrick; Fischer, Ingo

doi:10.1039/d1cp04899f

Cited by 6 publications

(14 citation statements)

References 39 publications

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“…The lowest occupied molecular orbital (HOMO) is a doubly degenerate 1π orbital and its VIE is 11.29 eV. It agrees well with 11.31 ± 0.02 eV measured using CRF-PEPICO . The VIEs of other valence orbitals of this HBNH compound are well separated and spreading up to 26 eV.…”

Section: Resultssupporting

confidence: 83%

“…The first IE of the compound was measured using MS at 11.0 ± 0.1 eV and the same energy was calculated to be 10.62 eV using CCSD(T)/CBS . Similarly, no other valence IEs were available for iminoborane (HBNH), but the first IE of the compound was recently measured at 11.31 ± 0.02 eV using photoelectron–photoion coincidence spectroscopy (CRF-PEPICO), in agreement with an earlier calculation of 11.27 eV using the CCSD(T)/CBS method . To our knowledge, no CEBEs of the boron–nitrogen hydrides are available, neither in theory nor in experiment.…”

Section: Introductionsupporting

confidence: 75%

“…19 effect. However, in their most recent experimental study, Schleier et al 15 indicated that the Renner−Teller splitting in the X +2 Π′ state of HBNH gives rise to two sets of vibrational progressions, separated by 70 meV, which is ∼0.62% of the VIEs As a result, the present study does not consider such effects.…”

Section: Ionization Energies and Photoemission Spectra Of H N Bnh N (...mentioning

confidence: 69%

“…Theory with CCSD(T)/CBS, 10.62 eV d Experiment (CRF-PEPICO) 11.31 ± 0.02 eV . Theory with CCSD(T)/CBS, 11.27 eV …”

Section: Resultsmentioning

confidence: 99%

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Dehydrogenation of Ammonia Borane Impacts Valence and Core Electrons: A Photoemission Spectroscopic Study

Chong

Wang

2022

ACS Omega

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Ammonia borane (H 3 BNH 3 ) is a promising material for hydrogen storage and release. Dehydrogenation of ammonia borane produces small boron−nitrogen hydrides such as aminoborane (H 2 BNH 2 ) and iminoborane (HBNH). The present study investigates ammonia borane and its two dehydrogenated products for the first time using calculated photoemission spectra of the valence and core electrons. It is found that a significant decrease in the dipole moment was observed associated with the dehydration from 5.397 D in H 3 BNH 3 , to 1.942 D in H 2 BNH 2 , and to 0.083 D in HBNH. Such reduction in the dipole moment impacts properties such as hydrogen bonding, dihydrogen bonding, and their spectra. Dehydrogenation of H 3 BNH 3 impacts both the valence and core electronic structure of the boron−nitrogen hydrides. The calculated valence vertical ionization energy (VIE) spectra of the boron− nitrogen hydrides show that valence orbitals dominated by 2p-electrons of B and N atoms exhibit large changes, whereas orbitals dominated by s-electrons, such as (3a 1 4a 1 5a 1 /3σ4σ5σ) remain less affected. The first ionization energy slightly increases from 10.57 eV for H 3 BNH 3 to 11.29 eV for both unsaturated H 2 BNH 2 and HBNH. In core space, the oxidative dehydrogenation of H 3 BNH 3 affects the core electron binding energy (CEBE) of borane and nitrogen oppositely. The B1s binding energies increase from 194.01 eV in H 3 BNH 3 to 196.93 eV in HBNH, up by 2.92 eV, whereas the N1s binding energies decrease from 408.20 eV in H 3 BNH 3 to 404.88 eV in HBNH, dropped by 3.32 eV.

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Section: Resultssupporting

confidence: 83%

Section: Introductionsupporting

confidence: 75%

Section: Ionization Energies and Photoemission Spectra Of H N Bnh N (...mentioning

confidence: 69%

“…Theory with CCSD(T)/CBS, 10.62 eV d Experiment (CRF-PEPICO) 11.31 ± 0.02 eV . Theory with CCSD(T)/CBS, 11.27 eV …”

Section: Resultsmentioning

confidence: 99%

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Dehydrogenation of Ammonia Borane Impacts Valence and Core Electrons: A Photoemission Spectroscopic Study

Chong

Wang

2022

ACS Omega

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“…Vibrationally resolved reference spectra for methylpropargyl and methylallyl radicals help their direct detection in flames . Furthermore, larger hydrocarbon radicals such as benzyl, picolyl, xylyl, indenyl, and tropyl, along with exotic species such as methylbismuth, iminoborane, and lignin pyrolysis intermediates , have been successfully synthesized in situ and characterized utilizing ms-TPE spectra as well as Franck–Condon (FC) simulations. In most of the above-mentioned studies, FC simulations could reproduce the vibrational progressions in the spectra well.…”

Section: Introductionmentioning

confidence: 99%

Continuous Pyrolysis Microreactors: Hot Sources with Little Cooling? New Insights Utilizing Cation Velocity Map Imaging and Threshold Photoelectron Spectroscopy

Hemberger

Pan

et al. 2022

J. Phys. Chem. A

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Resistively heated silicon carbide microreactors are widely applied as continuous sources to selectively prepare elusive and reactive intermediates with astrochemical, catalytic, or combustion relevance to measure their photoelectron spectrum. These reactors also provide deep mechanistic insights into uni-and bimolecular chemistry. However, the sampling conditions and effects have not been fully characterized. We use cation velocity map imaging to measure the velocity distribution of the molecular beam signal and to quantify the scattered, rethermalized background sample. Although translational cooling is efficient in the adiabatic expansion from the reactor, the breakdown diagrams of methane and chlorobenzene confirm that the molecular beam component exhibits a rovibrational temperature comparable with that of the reactor. Thus, rovibrational cooling is practically absent in the expansion from the microreactor. The high rovibrational temperature also affects the threshold photoelectron spectrum of both benzene and the allyl radical in the molecular beam, but to different degrees. While the extreme broadening of the benzene TPES suggests a complex ionization mechanism, the allyl TPES is in fact consistent with an internal temperature close to that of the reactor. The background, room-temperature spectra of both are superbly reproduced by Franck−Condon simulations at 300 K. On the one hand, this leads us to suggest that room-temperature reference spectra should be used in species identification. On the other hand, analysis of the allyl iodide pyrolysis data shows that iodine atoms often recombine to form molecular iodine on the chamber surfaces. Such sampling effects may distort the chemical composition of the scattered background with respect to the molecular beam signal emanating directly from the reactor. This must be considered in quantitative analyses and kinetic modeling.

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Ammonia Borane, NH₃BH₃: A Threshold Photoelectron–Photoion Coincidence Study of a Potential Hydrogen‐Storage Material

Schleier

Gerlach

Mukhopadhyay

et al. 2022

Chemistry A European J

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We have investigated the photoionization of ammonia borane (AB) and determined adiabatic ionization energy to be 9.26 � 0.03 eV for the X + 2 E ! X 1 A 1 transition. Although the threshold photoelectron spectrum appears at first glance to be similar to the one of the isosteric ethane, the electronic situation differs markedly, due to different orbital energies. In addition, an appearance energy AE 0K -(NH 3 BH 3 , NH 3 BH 2 + ) = 10.00 � 0.03 eV has been determined, corresponding to the loss of a hydrogen atom at the BH 3 -site. From the data, a 0 K bond dissociation energy for the BÀ H bond in the cation of 71.5 � 3 kJ mol À 1 was derived, whereas the one in the neutral compound has been estimated to be 419 � 10 kJ mol À 1 .

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Threshold photoelectron spectroscopy of iminoborane, HBNH

Abstract: We report the mass-selected threshold photoelectron spectrum (ms-TPES) of iminoborane (HBNH), generated by pyrolysis of borazine. The adibatic ionization energy (IE) of the X+ 2Π <-- X 1Σ transition was...

Cited by 6 publications

References 39 publications

Dehydrogenation of Ammonia Borane Impacts Valence and Core Electrons: A Photoemission Spectroscopic Study

Dehydrogenation of Ammonia Borane Impacts Valence and Core Electrons: A Photoemission Spectroscopic Study

Continuous Pyrolysis Microreactors: Hot Sources with Little Cooling? New Insights Utilizing Cation Velocity Map Imaging and Threshold Photoelectron Spectroscopy

Ammonia Borane, NH₃BH₃: A Threshold Photoelectron–Photoion Coincidence Study of a Potential Hydrogen‐Storage Material

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Threshold photoelectron spectroscopy of iminoborane, HBNH

Abstract: We report the mass-selected threshold photoelectron spectrum (ms-TPES) of iminoborane (HBNH), generated by pyrolysis of borazine. The adibatic ionization energy (IE) of the X+ 2Π <-- X 1Σ transition was...

Cited by 6 publications

References 39 publications

Dehydrogenation of Ammonia Borane Impacts Valence and Core Electrons: A Photoemission Spectroscopic Study

Dehydrogenation of Ammonia Borane Impacts Valence and Core Electrons: A Photoemission Spectroscopic Study

Continuous Pyrolysis Microreactors: Hot Sources with Little Cooling? New Insights Utilizing Cation Velocity Map Imaging and Threshold Photoelectron Spectroscopy

Ammonia Borane, NH3BH3: A Threshold Photoelectron–Photoion Coincidence Study of a Potential Hydrogen‐Storage Material

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Ammonia Borane, NH₃BH₃: A Threshold Photoelectron–Photoion Coincidence Study of a Potential Hydrogen‐Storage Material