Radical Cation of 1,3-Butadiene:  Resonance Raman Spectrum of the <i>h</i><sub>6</sub> Isotopomer

Keszthelyi, Tamás; Wilbrandt, R.; Bally, Thomas

doi:10.1021/jp9618385

Cited by 20 publications

(26 citation statements)

References 48 publications

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“…It appears that the area of molecular structure and vibrational spectra of organic radical cations forms another domain where the gradient-corrected DFT methodology can be applied very successfully. 59, [62][63][64][65] The N-ring stretching vibration is in all cases a complex vibration, with various local modes contributing. The UBLYP calculations predict its frequency best.…”

Section: Discussionmentioning

confidence: 99%

Vibrational Spectra of N,N-Dimethylaniline and Its Radical Cation. An Interpretation Based on Quantum Chemical Calculations

1996

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The resonance Raman spectrum of the radical cation of N,N-dimethylaniline (DMA) has been remeasured, and different types of ab initio calculations have been performed to interpret the vibrational spectra of this species and the deuteriated isotopomers previously studied by Poizat et al. (J. Chem. Phys. 1989, 90, 4697). Density functional methods (UBLYP/6-31G*) give results superior to those of Hartree-Fock calculations for the vibrational frequencies of the radical cation of DMA. The same level of theory was also successfully applied to the vibrational spectrum of aniline. CASSCF calculations were used to study the potential energy surfaces of the lowest excited states of the radical cation of DMA, allowing the estimation of resonance Raman intensities. For the neutral DMA conventional HF/6-31G* calculations allow a straightforward interpretation of the infrared and Raman spectra. The calculations lead to revision of some of the previous empirical assignments.

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Section: Discussionmentioning

confidence: 99%

Vibrational Spectra of N,N-Dimethylaniline and Its Radical Cation. An Interpretation Based on Quantum Chemical Calculations

1996

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“…Apart from general scientific interest, the properties of radical ions in condensed media are also important in the context of materials science and technology. For the past few years we have been involved in the experimental and theoretical investigation of the radical cations of short linear conjugated polyenes [1][2][3][4][5], and of amine-based electron donors such as N,N-dimethylaniline [6] and N,N-dimethylpiperazine [7]. The interest in the properties of polyene radical cations is in part *Corresponding author.…”

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confidence: 99%

The Radical Cation of Bithiophene:An Experimental and TheoreticalStudy

et al. 1999

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The electronic absorption spectrum of the bithiophene radical cation prepared by γ-irradiation in a glassy Freon matrix is presented, together with the Raman spectra excited at 550 and 425 nm, in resonance with the two absorption bands. The 425 nm excited Raman spectrum was also recorded in a room temperature acetonitrile solution, in this case the radical cation was generated via a photoinduced electron transfer reaction. The resonance Raman spectra were interpreted with the help of density functional theory calculations. The results indicate the existence of at least two rotamers of the bithiophene radical cation. The time-domain method was applied to the simultaneous fitting of the absorption and resonance Raman spectra.

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“…The total 4 photon energy would then be 15.48 eV, indicating an ionization process requiring 13.86 eV to produce the 1.62 eV electron. 13.86 eV matches the appearance energy of the fragment C 4 H 4 ϩ ͑13.84Ϯ0.07 eV͒ from butadiene. 15 Despite the close energetic match, this above-threshold dissociative ionization mechanism seems unlikely.…”

Section: B Mpi Time-of-flight Photoelectron Spectramentioning

confidence: 59%

Multiphoton ionization and photoelectron spectroscopy of 1,3-trans-butadiene via its 3dπ Rydberg state

Anderson

2001

The Journal of Chemical Physics

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Articles you may be interested inVacuum ultraviolet pulsed field ionization-photoelectron and infrared-photoinduced Rydberg ionization study of trans-1,3-butadieneThe role of symmetry and optical selection rules in revealing the molecular structure of the lowest Rydberg and ionic states of the 1,4-diazabicyclo[2.2.2]octane-Ar n (n=1,2,3) van der Waals complexes J. Chem. Phys. 120, 7894 (2004); 10.1063/1.1691765 (3+1) -resonantly enhanced multiphoton ionization-photoelectron spectroscopy of the (3d-4s) supercomplex of acetylene: The geometry of the E state revisited through experiment and theory Resonance-enhanced multiphoton ionization ͑REMPI͒ and photoelectron spectroscopy ͑PES͒, have been used to study the 1 A g (3d) Rydberg state of 1,3-trans-butadiene in the two photon energy range from 61 000 to 66 400 cm Ϫ1 . The 1 A g (3d) spectrum is dominated by the 4 Ј , 6 Ј , and 9 Ј vibrational modes, with some excitation of the 8 Ј mode, as well. Photoelectron spectroscopy shows that the dominant ionization pathways are diagonal, i.e., they produce cations in the same vibrational level that was populated in the Rydberg state. Weaker off-diagonal ionization is also observed, with excitation of the 4 ϩ , 6 ϩ , and 9 ϩ modes. The relative intensities of diagonal and off-diagonal PES bands are observed to be strongly dependent on the angle between the laser polarization and the detection axis. It is possible to use REMPI to generate state-selected cations, however, the nascent ions are quite efficiently photodissociated by the REMPI laser.

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Radical Cation of 1,3-Butadiene: Resonance Raman Spectrum of the h₆ Isotopomer

Cited by 20 publications

References 48 publications

Vibrational Spectra of N,N-Dimethylaniline and Its Radical Cation. An Interpretation Based on Quantum Chemical Calculations

Vibrational Spectra of N,N-Dimethylaniline and Its Radical Cation. An Interpretation Based on Quantum Chemical Calculations

The Radical Cation of Bithiophene:An Experimental and TheoreticalStudy

Multiphoton ionization and photoelectron spectroscopy of 1,3-trans-butadiene via its 3dπ Rydberg state

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Radical Cation of 1,3-Butadiene: Resonance Raman Spectrum of the h6 Isotopomer

Cited by 20 publications

References 48 publications

Vibrational Spectra of N,N-Dimethylaniline and Its Radical Cation. An Interpretation Based on Quantum Chemical Calculations

Vibrational Spectra of N,N-Dimethylaniline and Its Radical Cation. An Interpretation Based on Quantum Chemical Calculations

The Radical Cation of Bithiophene:An Experimental and TheoreticalStudy

Multiphoton ionization and photoelectron spectroscopy of 1,3-trans-butadiene via its 3dπ Rydberg state

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Radical Cation of 1,3-Butadiene: Resonance Raman Spectrum of the h₆ Isotopomer