Vacuum ultraviolet laser pulsed field ionization photoelectron study of <i>cis</i>-2-butene

Woo, H. K.; Zhan, Jiping; Lau, Kai‐Chung; Ng, C. Y.; Cheung, Yu‐San

doi:10.1063/1.1473663

Cited by 31 publications

(31 citation statements)

References 17 publications

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“…The calculated values for the 0 K E 0 (2-C 3 H 7 + ) from 2-C 3 H 7 Cl are 11.061 and 11.048 eV obtained with ZPVE corrections at the MP2 and B3LYP levels, respectively. Considering the previous comparisons of similar calculations with highly precise PFI measurements, [18][19][20][21][22][23] we may conclude that this calculation predicts a value of 11.054 ± 0.020 eV for the 0 K AE(2-C 3 H 7 + ) from 2-C 3 H 7 Cl.…”

Section: Theoretical Calculationsmentioning

confidence: 62%

“…With the advance in computer capacity, it is now possible to perform high-level ab initio quantum chemical calculations for mid-size molecules such as 2-C 3 H 7 Cl. In recent studies, [18][19][20][21][22][23] we find that the complete basis set (CBS) extrapolation method at the couple cluster with single and double excitations, plus a quasi-perturbative triple excitations [CCSD(T, Full)/CBS] level of theory, 24 together with high-level corrections, generally yields reliable theoretical IE and AE predictions to within ± 20 meV compared with experimental results obtained in highly precise PFI studies. To provide insight into the reliability of the experimental AE measurements, we have also calculated the 0 K AE(2-C 3 H 7 + ) from 2-C 3 H 7 Cl at the CCSD(T, full/CBS) level with high-level corrections.…”

Section: The C 3 H 7 + Appearance Energy From 2-iodopropane and 2-chlmentioning

confidence: 98%

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The C₃H₇⁺ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence

Brooks

Lau

et al. 2004

Eur J Mass Spectrom (Chichester)

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The dissociation onset for halogen atom loss was investigated for 2-iodo and 2-chloropropane ions using a newly developed threshold photoelectron photoion coincidence (TPEPICO) technique that suppresses the effects of hot electrons. This study was undertaken in order to resolve current discrepancies concerning these onsets in the literature. The 0 K dissociation thresholds were determined to be 9.818 ± 0.010 and 11.036 ± 0.010 eV for 2-C 3 H 7 I and 2-C 3 H 7 Cl, respectively. These numbers agree quite well with photoionization and a mass analyzed threshold ionization (MATI) study, but are significantly lower than onsets measured by the much higher resolution pulsed field ionization PEPICO method. The derived C 3 H 7 + heat of formation at 298 K is 803.9 ± 1.5 kJ mol-1 , and a more precise value for the 298 K 2-iodopropane heat of formation is-40.8 ± 1.3 kJ mol-1. The derived proton affinity of propene is 746.1 kJ mol-1. We have also performed a high-level ab initio calculation on the 0 K dissociation limit, E 0 , for C 3 H 7 + from C 3 H 7 Cl at the CCSD(T)/CBS level of theory with high-level corrections. The theoretical prediction of 11.048-11.061 eV for E 0 (C 3 H 7 +) from C 3 H 7 Cl is found to be consistent with the current experimental value.

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Section: Theoretical Calculationsmentioning

confidence: 62%

Section: The C 3 H 7 + Appearance Energy From 2-iodopropane and 2-chlmentioning

confidence: 98%

The C₃H₇⁺ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence

Brooks

Lau

et al. 2004

Eur J Mass Spectrom (Chichester)

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“…The pulsed beam thus formed is skimmed by a conical skimmer before entering the photoionization/ photoexcitation ͑PI/PEX͒ region of the photoion and photoelectron apparatus. 23,24 On the basis of spectral simulation of rotationally resolved single-photon VUV laser PFI-PE spectra for the 2 n ͑n =0-3͒ vibrational bands of NH 3 + ͑X ͒, 18 we estimate that the rotational temperature for NH 3 achieved in the supersonic expansion is Ϸ20 K.…”

Section: Methodsmentioning

confidence: 99%

“…[19][20][21][22][23][24] Briefly, the apparatus consists of a pulsed ͑30 Hz͒ tunable VUV laser system, a pulsed ͑15 Hz͒ IR optical parametric oscillator/amplifier ͑IR-OPO/A͒, a pulsed molecular-beam source, a TOF electron spectrometer for PFI-PE detection, and a TOF mass spectrometer for ion detection. The electron spectrometer and mass spectrometer are each equipped with a microchannel-plate ͑MCP͒ detector for the detection of electrons and ions, respectively.…”

Section: Methodsmentioning

confidence: 99%

A two-color infrared-vacuum ultraviolet laser pulsed field ionization photoelectron study of NH3

Bahng

Xing

Baek

et al. 2005

The Journal of Chemical Physics

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We have observed fully rotationally resolved transitions of the photoelectron vibrational bands 2(4), 2(5), 1(1)2(1), and 1(1)2(3) for ammonia cation (NH3+) by two-color infrared (IR)-vacuum ultraviolet (VUV)- pulsed field-ionization photoelectron (PFI-PE) measurements. By preparing an intermediate rovibrational state of neutral NH(3) with a known parity by IR excitation followed by VUV-PFI-PE measurements, we show that the photoelectron parity can be determined unambiguously. The IR-VUV-PFI-PE measurement of the 2(4) band clearly reveals the formation of both even and odd l states for the photoelectrons, where l is the orbital angular momentum quantum number. This observation is consistent with the conclusion that the lack of inversion symmetry for NH3 and NH3+ allows odd/even l mixings, rendering the production of both odd and even l states for the photoelectrons. Evidence is also found, indicating that the photoionization transitions with DeltaK=0 are strongly favored compared to that with DeltaK=3. For the 2(5), 1(1)2(1), and 1(1)2(3) bands, only DeltaK=0 transitions for the production of even l photoelectron states from the J'K'=2(0) rotational level of NH3(nu1=1) are observed. The preferential formation of even l photoelectron states for these vibrational bands is attributed to the fact that the DeltaK=0 transitions for the formation of odd l photoelectron states from the 2(0) rotational level of NH3(nu1=1) are suppressed by the constraint of nuclear-spin statistics. In addition to information obtained on the photoionization dynamics of NH3, this experiment also provides a more precise value of 3232+/-10 cm-1 for the nu1+ (N-H stretch) vibrational frequency of NH3+.

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“…The CO 2 and 1-butene 0 K enthalpies of formation are well-known at −393.1 ± 0.0 and 21.0 ± 0.4 kJ mol −1 , respectively, 64 whereas the 1-butene ionization energy is less well-defined at 9.55 ± 0.06 eV. 65 We compare accurately measured cis-and trans-2-butene ionization energies of 9.125 and 9.128 eV, respectively, by ZEKE spectroscopy by Ng et al 66,67 with CBS-APNO and W1BD-computed ones. The CBS-APNO ones are in error by 0.046 and 0.049 eV, whereas the W1BD IEs differ by 0.005 and 0.004 eV, respectively.…”

Section: Computational Sectionmentioning

confidence: 84%

Photoionization of Two Potential Biofuel Additives: γ-Valerolactone and Methyl Butyrate

et al. 2021

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The photoionization of two potential biofuel additives, γ-valerolactone (GVL, C 5 H 8 O 2 ) and methyl butyrate (MB, C 5 H 10 O 2 ) has been studied by imaging photoelectron photoion coincidence spectroscopy (iPEPICO) at the VUV beamline of the Swiss Light Source (SLS). The vibrational fine structure in the photoelectron spectrum is compared with a Franck−Condon simulation for the electronic ground-state band of the GVL cation. In the lowest energy dissociative photoionization channel of GVL, CO 2 is lost, resulting in a 1-butene fragment ion with a 0 K appearance energy of E 0 = 10.35 ± 0.01 eV. A newly calculated 1-butene ionization energy of 9.595 ± 0.015 eV establishes the reverse barrier height to CO 2 loss as 66.6 ± 4.3 kJ mol −1 . Methyl butyrate cations undergo McLafferty rearrangement, which explains the missing ion signal at the computed adiabatic ionization energy of 9.25 eV. After H transfer, ethylene is lost in the lowest energy dissociation channel to yield the methyl acetate enol ion at E 0 = 10.24 ± 0.04 eV. This value connects the energetics of methyl butyrate with that of methyl acetate enol ion, which is established atParallel to ethylene loss, methyl loss is also observed from the enol tautomer of the parent ion. Both samples exhibit low-energy nonstatistical dissociative ionization channels. In GVL, the methyl-loss abundance rises quickly but levels off suddenly in the energy range of the first electronically excited states, indicating nonstatistical competition between CH 3 and CO 2 loss. In MB, the major parallel dissociation channel is the loss of a methoxy radical. Calculations indicate that McLafferty rearrangement is inhibited on the excited-state surface. Indeed, breakdown curve modeling of this and a sequential CO-loss channel confirms a second statistical regime in dissociative photoionization, decoupled from ethylene loss.

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Vacuum ultraviolet laser pulsed field ionization photoelectron study of cis-2-butene

Cited by 31 publications

References 17 publications

The C₃H₇⁺ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence

The C₃H₇⁺ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence

A two-color infrared-vacuum ultraviolet laser pulsed field ionization photoelectron study of NH3

Photoionization of Two Potential Biofuel Additives: γ-Valerolactone and Methyl Butyrate

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Vacuum ultraviolet laser pulsed field ionization photoelectron study of cis-2-butene

Cited by 31 publications

References 17 publications

The C3H7+ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence

The C3H7+ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence

A two-color infrared-vacuum ultraviolet laser pulsed field ionization photoelectron study of NH3

Photoionization of Two Potential Biofuel Additives: γ-Valerolactone and Methyl Butyrate

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The C₃H₇⁺ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence

The C₃H₇⁺ Appearance Energy from 2-Iodopropane and 2-Chloropropane Studied by Threshold Photoelectron Photoion Coincidence