Photoelectron spectra of vinyl and allyl halides

Mines, G. W.; Thompson, H. W.

doi:10.1016/0584-8539(73)80201-6

Cited by 38 publications

(17 citation statements)

References 13 publications

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“…In summary, the seven identified Rydberg series observed in this study fit very well to the Rydberg formula. We have taken the average IE value of the seven series to be 79 194 ± 17 cm À1 (9.819 ± 0.002 eV) as the adiabatic IE, which is in excellent agreement with the values obtained previously from various methods [1,2,4,5,7,8,12].…”

Section: Resultssupporting

confidence: 86%

“…Spectroscopic investigations of the excited electronic states and potential energy surfaces of polyatomic molecules are of fundamental importance to study molecular photochemical reactions. The spectroscopic [1][2][3][4][5][6][7][8][9][10][11][12] and dissociation dynamical [13][14][15][16][17][18] studies of vinyl bromide (C 2 H 3 Br, abbreviated as VB hereafter) have been extensively studied in the past decades. Following our previous investigations of vinyl chloride (C 2 H 3 Cl) ranging from its first excited electronic state to the first ionization energy (IE) [19][20][21], we are now extending the spectroscopic study to VB, an analogue to vinyl chloride with a halogen substitution.…”

Section: Introductionmentioning

confidence: 99%

“…In an early spectroscopic study, Chadwick et al [1] used photoelectron spectroscopy (PES) to obtain the spectra of VB, 1,2-dibromoethylene, and 2-bromopropene, from which the interaction between lone-pair electrons located at the Br atom and p-bonding electrons was studied. Mines and Thompson [2] also applied PES in the range of 6-21 eV to determine the IEs of vinyl halides and allyl halides. Schander and Russell [3] reported the vacuum ultraviolet (VUV) absorption spectrum of VB at 110-210 nm, and identified two Rydberg series, p fi ns and p fi np, convergent to the first IE of 79 860 cm À1 .…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

High-lying Rydberg states of vinyl bromide studied by two-photon resonant ionization spectroscopy

Chuang¹,

Chen²,

Wu³

et al. 2004

Chemical Physics Letters

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Section: Resultssupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

High-lying Rydberg states of vinyl bromide studied by two-photon resonant ionization spectroscopy

Chuang¹,

Chen²,

Wu³

et al. 2004

Chemical Physics Letters

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“…Figure B gives a more complex example of the m / z = 58.042 (C 3 H 6 O) peak with 9 possible isomers: acetone, propanal, oxetane, methyloxirane, cyclopropanol, 1-propen-1-ol, 1-propen-2-ol, 2-propen-1-ol, and methyl vinyl ether. The measured TPE and PI spectra in Figure B are reproduced well up to 10 eV by the reference spectra of 1-propen-2-ol and acetone, , whereas nearly all other possible C 3 H 6 O species can be ruled out on the basis of their PI , or TPE , spectra. The absolute PI spectrum of 1-propen-2-ol was measured in this work (see Table S2), and the TPE spectrum was calculated.…”

Section: Resultsmentioning

confidence: 58%

To Boldly Look Where No One Has Looked Before: Identifying the Primary Photoproducts of Acetylacetone

et al. 2019

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We investigate the gas-phase photochemistry of the enolone tautomer of acetylacetone (pentane-2,4-dione) following S2(ππ*) ← S0 excitation at λ = 266 and 248 nm, using three complementary time-resolved spectroscopic methods. Contrary to earlier reports, which claimed to study one-photon excitation of acetylacetone and found OH and CH3 as the only important gas-phase products, we detect 15 unique primary photoproducts and demonstrate that five of them, including OH and CH3, arise solely by multiphoton excitation. We assign the one-photon products to six photochemical channels and show that the most significant pathway is phototautomerization to the diketone form, which is likely an intermediate in several of the other product channels. Furthermore, we measure the equilibrium constant of the tautomerization of the enolone to diketone on S0 from 320 to 600 K and extract ΔH = 4.1 ± 0.3 kcal·mol–1 and ΔS = 6.8 ± 0.5 cal·mol–1·K–1 using a van’t Hoff analysis. We correct the C–OH bond dissociation energy in acetylacetone, previously determined as 90 kcal·mol–1 by theory and experiment, to a new value of 121.7 kcal·mol–1. Our experiments and electronic structure calculations provide evidence that some of the product channels, including phototautomerization, occur on S0, while others likely occur on excited triplet surfaces. Although the large oscillator strength of the S2 ← S0 transition results from the (ππ*) excitation of the CCCO backbone, similar to conjugated polyenes, the participation of triplets in the dissociation pathways of acetylacetone appears to have more in common with ketone photochemistry.

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“…Recently, we have analyzed the 2ϩ1 resonanceenhanced multiphoton ionization ͑REMPI͒ spectra of VC in the energy region of 7.3-10 eV, from which the adiabatic ionization energy ͑AIE͒ of VC is determined to be 80 720Ϯ6 cm Ϫ1 ͑10.0080Ϯ0.0007 eV͒, 29,30 in agreement with that obtained by photoelectron spectroscopy. [31][32][33][34][35][36] Our work, in conjunction with a previous REMPI study on VC by Williams and Cool, 37 provide valuable insights into the excited states involved in the photodissociation dynamics of VC at 7.3-10 eV. Below 7.3 eV, the absorption spectrum of VC reported by Berry 14 shows a broad and continuous band, yet with some weak features.…”

Section: Introductionmentioning

confidence: 59%

Ab initio calculations of low-lying electronic states of vinyl chloride

Chang¹,

Chen²

2002

The Journal of Chemical Physics

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The equilibrium geometries, vibrational frequencies, excitation energies, and oscillator strengths of vinyl chloride in the ground and five lowest-lying excited singlet states have been calculated using MP2, CIS, CASSCF, and MRCI methods with the 6-311ϩϩG** basis set. The geometries and vibrational frequencies of the ground and excited states are utilized to compute Franck-Condon factors. Calculated vibronic spectra for the transitions from the ground state to these five excited states are in agreement with experiment at 52 500-60 000 cm Ϫ1 , with major contributions from the Ã (1 1 AЉ)←X (1 1 AЈ) and C (2 1 AЈ)←X (1 1 AЈ) transitions. In this study, two spin-forbidden transitions of b (1 3 AЉ)←X (1 1 AЈ) and c (2 3 AЉ)←X (1 1 AЈ) are calculated to locate in 45 000-54 000 cm Ϫ1 , and could be responsible for the observed one-photon absorption spectrum due to an intensity borrowing caused by the spin-orbit coupling of the Cl atom. Based on calculation, we speculate that upon the excitation of vinyl chloride at 193 nm the b (1 3 AЉ) or c (2 3 AЉ) excited state, instead of the ͑,*͒, is initially prepared prior to the subsequent photodissociation processes.

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Photoelectron spectra of vinyl and allyl halides

Cited by 38 publications

References 13 publications

High-lying Rydberg states of vinyl bromide studied by two-photon resonant ionization spectroscopy

High-lying Rydberg states of vinyl bromide studied by two-photon resonant ionization spectroscopy

To Boldly Look Where No One Has Looked Before: Identifying the Primary Photoproducts of Acetylacetone

Ab initio calculations of low-lying electronic states of vinyl chloride

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