Valence-Shell Ionization Potentials of Halomethanes by Photoelectron Spectroscopy. I CH3Cl, CH3Br, CH3I. Vibrational Frequencies and Vibronic Interaction in CH3Br+ and CH3Cl+

Ragle, J. L.; Stenhouse, I. A.; Frost, D. C.; McDowell, C. A.

doi:10.1063/1.1673762

Cited by 92 publications

(26 citation statements)

References 14 publications

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“…With the ANO′ basis set, described below, the CASPT2 calculations gave a vertical ionization potential of 11.14 eV, in excellent agreement with experimental values of 11.17 ( 2 E 3/2 ) and 11.25 eV ( 2 E 1/2 ). 22 The CIS calculations were performed using the 6-31+G contracted Gaussian basis set 23 as well as with a 6-31+G*+2s2pd basis set, formed by adding to the 6-31+G basis set diffuse s (two), p (two), and d (one) primitive Gaussian-type functions centered on the Cl atom. The exponents of the supplemental diffuse functions were obtained by optimizing the low-lying virtual orbitals from Hartree-Fock calculations on the ground state cation of CH 3 Cl.…”

Section: Methodsmentioning

confidence: 99%

Low-Lying Electronically Excited States of CH₃Cl: Comparison of Theory and Experiment

1996

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Electron energy loss spectroscopy is used to determine the energies of the low-lying singlet and triplet states of methyl chloride. The experimental results are interpreted with the aid of ab initio calculations. The triplet n f σ*(C-Cl) state is found to lie about 0.4 eV below the singlet n f σ*(C-Cl) state. Both the electron energy loss measurements and the calculations indicate that it is possible to distinguish singlet and triplet states derived from the n f 4s and n f 4p excitations.

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Section: Methodsmentioning

confidence: 99%

Low-Lying Electronically Excited States of CH₃Cl: Comparison of Theory and Experiment

1996

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“…spectrum of which is well documented (4)(5)(6)(7)(8). We will give a brief description of this spectrum since the succeeding spectra may then be discussed with reference to it.…”

Section: Normal Lodoalkanesmentioning

confidence: 99%

“…The p.e, spectrum of iodomethane is well known (4)(5)(6)(7)(8). It is included here for com~leteness and since correlations will be drawn with it in the discussion of the remaining spectra.…”

Section: Introductionmentioning

confidence: 99%

The High Resolution Photoelectron Spectra of Some Iodoalkanes, Iodocycloalkanes, Iodoalkenes, and Fluoroiodohydrocarbons

Boschi¹,

Salahub²

1974

Can. J. Chem.

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The high resolution photoelectron spectra for the following iodine-containing molecules have been measured: iodomethane, iodoethane, 1-iodopropane, 1-iodobutane, l-iodopentane, 1-iodohexane, 2-methyl-1-iodopropane, 3-methyl-1-iodobutane, 2-iodopropane, iodocyclopentane, iodocyclohexane, 2-methyl-2-iodopropane, trifluoroiodomethane, 2,2,2-trifluoro-1-iodoethane, pentafluoroiodoethane, 3,3,3,2,2,1,1-heptafluoro-1-iodopropane, iodobenzene, pentafluoroiodobenzene, vinyl iodide, ally1 iodide. The spectra are discussed in terms of extended Hiickel ( E H ) molecular orbital calculations and of the qualitative changes upon variation of the alkyl group.On a mesurt les spectres de photo6lectrons i haute rtsolution des iodures suivantes: iodomithane, iodotthane, iodo-1 propane, iodo-l butane, iodo-1 pentane, iodo-1 hexane, methyl-2 iodo-1 propane, mtthyl-3 iodo-1 butane, iodo-2 propane, iodocyclopentane, iodocyclohexane, mtthyl-2 iodo-2 propane, trifluoroiodomtthane, trifluoro-2,2,2 iodo-1 tthane, pentafluoroiodotthane, heptafluoro-l,l,2,2,3,3,3 iodo-1 propane, iodobenzsne, pentafluoroiodobenzGme, iodure de vinyle et iodure d'allyle. On discute les spectres a I'aide des calculs d'orbitales molCculaires dans l'approximation de Hiickel ttendue e t aussi en fonction des changements qualitatifs lors de la variation du groupe alkyle.[Traduit par le journal]Can.

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“…The A component of the effective P state (corresponding to the σ C−I bonding orbital) leads to an excited electronic state (Ã + 2 A 1 ) located 2.65 eV above theX + 2 E ground state. 4 This separation is much larger than the spinorbit splitting, so that one can assume in good approximation that¯2…”

Section: A Vibronic and Spin-orbit Coupling In The 2 E Electronic Grmentioning

confidence: 99%

“…He I and He II photoelectron a) Electronic mail: feme@xuv.phys.chem.ethz.ch. spectra have provided information on the vibronic structure of theX + 2 E ground state [4][5][6][7][8][9][10][11] from which the general features of the Jahn-Teller effect have been derived, including a qualitative understanding of the role of the spin-orbit coupling. Theoretical studies of the Jahn-Teller effect have been reported that account for the vibronic structure observed in these He I photoelectron spectra.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

Grütter

Michaud

Merkt

2011

The Journal of Chemical Physics

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The high-resolution single-photon pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the \documentclass[12pt]{minimal}\begin{document}$\tilde{\rm {X}}^+$\end{document}X̃+ 2\documentclass[12pt]{minimal}\begin{document}$\rm {E_{3/2}}\leftarrow \tilde{\rm {X}}\, ^1{\rm A}_1$\end{document}E3/2←X̃1A1 transition of CH3I and CD3I have been recorded. The spectral resolution of better than 0.15 cm−1 enabled the observation of the rotational structure. CH3I+ and CD3I+ are subject to a weak \documentclass[12pt]{minimal}\begin{document}$\rm {E}\otimes \rm {e}$\end{document}E⊗e Jahn–Teller effect and strong spin–orbit coupling. The treatment of the rovibronic structure of the photoelectron spectra in the corresponding spin double group, \documentclass[12pt]{minimal}\begin{document}$\rm {C_{3v}^2(M)}$\end{document}C3v2(M), including the effects of the spin–orbit interaction and the vibrational angular momentum, allowed the reproduction of the experimentally observed transitions with spectroscopic accuracy. The relevant spin–orbit and linear Jahn–Teller coupling parameters of the \documentclass[12pt]{minimal}\begin{document}$\tilde{\rm {X}}^+$\end{document}X̃+ ground state were derived from the analysis of the spectra of the two isotopomers, and improved values were obtained for the adiabatic ionization energies [\documentclass[12pt]{minimal}\begin{document}${E_{\rm {I}}(\rm {CH}_3\rm {I})}/hc =76931.35(20)$\end{document}EI( CH 3I)/hc=76931.35(20) cm−1 and \documentclass[12pt]{minimal}\begin{document}${E_{\rm {I}}(\rm {CD}_3\rm {I})}/hc=76957.40(20)$\end{document}EI( CD 3I)/hc=76957.40(20) cm−1] and the rotational constants of the cations. Rovibronic photoionization selection rules were derived for transitions connecting neutral states following Hund's-case-(b)-type angular momentum coupling and ionic states following Hund's-case-(a)-type coupling. The selection rules, expressed in terms of the angular momentum projection quantum number P, account for all observed transitions and provide an explanation for the nonobservation of several rotational sub-bands in the mass-analyzed threshold-ionization spectra of \documentclass[12pt]{minimal}\begin{document}$\rm {CH}_3\rm {I}$\end{document} CH 3I and \documentclass[12pt]{minimal}\begin{document}$\rm {CD}_3\rm {I}$\end{document} CD 3I reported recently by Lee et al. [J. Chem. Phys. 128, 044310 (2008)].

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Valence-Shell Ionization Potentials of Halomethanes by Photoelectron Spectroscopy. I CH3Cl, CH3Br, CH3I. Vibrational Frequencies and Vibronic Interaction in CH3Br+ and CH3Cl+

Cited by 92 publications

References 14 publications

Low-Lying Electronically Excited States of CH₃Cl: Comparison of Theory and Experiment

Low-Lying Electronically Excited States of CH₃Cl: Comparison of Theory and Experiment

The High Resolution Photoelectron Spectra of Some Iodoalkanes, Iodocycloalkanes, Iodoalkenes, and Fluoroiodohydrocarbons

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

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Valence-Shell Ionization Potentials of Halomethanes by Photoelectron Spectroscopy. I CH3Cl, CH3Br, CH3I. Vibrational Frequencies and Vibronic Interaction in CH3Br+ and CH3Cl+

Cited by 92 publications

References 14 publications

Low-Lying Electronically Excited States of CH3Cl: Comparison of Theory and Experiment

Low-Lying Electronically Excited States of CH3Cl: Comparison of Theory and Experiment

The High Resolution Photoelectron Spectra of Some Iodoalkanes, Iodocycloalkanes, Iodoalkenes, and Fluoroiodohydrocarbons

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

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Low-Lying Electronically Excited States of CH₃Cl: Comparison of Theory and Experiment

Low-Lying Electronically Excited States of CH₃Cl: Comparison of Theory and Experiment