The radical cation and lowest Rydberg states of 1,4-diaza[2.2.2]bicyclooctane (DABCO)

Gurusamy Balakrishnan, T. Keszthelyi, Robert Wilbrandt, Jurriaan M. Zwier, Albert M. Brouwer, Wybren Jan Buma

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The radical cation and the two lowest excited singlet Rydberg states of DABCO (1,4-diazabicyclo[2.2.2]-octane) are studied. Experimentally, the radical cation of DABCO is generated by either laser flash photolysis in solution at room temperature or by γ-irradiation in a Freon glass at 77 K, and its electronic absorption and resonance Raman spectra in these two media are reported. The present resonance Raman spectra differ substantially from previous reports given in the literature, and it is concluded that a number of bands attributed previously to the DABCO radical cation are due to other species. Theoretically, the absorption and resonance Raman spectra are interpreted on the basis of density functional theory (DFT; B3LYP/6-31G(d)) calculations and wave packet propagation methods. The same DFT calculations are used to interpret excitation and multiphoton ionization spectra of the two lowest singlet Rydberg states, making use of the close similarity between a Rydberg state and its ionic core. From the combined results it is concluded that DFT calculations with a relatively modest basis set provide a valuable framework to predict potential energy surfaces of radical cations and Rydberg states in terms of minima and Hessians.

Original languageEnglish
Pages (from-to)1834-1841
Number of pages8
JournalJournal of Physical Chemistry A
Volume104
Issue number9
Publication statusPublished - Mar 9 2000

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Rydberg states
Cations
Discrete Fourier transforms
Raman scattering
cations
Raman spectra
Chlorofluorocarbons
freon
Wave packets
Potential energy surfaces
Photolysis
octanes
wave packets
Ionization
Density functional theory
flash
photolysis
potential energy
Irradiation
density functional theory

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Balakrishnan, G., Keszthelyi, T., Wilbrandt, R., Zwier, J. M., Brouwer, A. M., & Buma, W. J. (2000). The radical cation and lowest Rydberg states of 1,4-diaza[2.2.2]bicyclooctane (DABCO). Journal of Physical Chemistry A, 104(9), 1834-1841.

The radical cation and lowest Rydberg states of 1,4-diaza[2.2.2]bicyclooctane (DABCO). / Balakrishnan, Gurusamy; Keszthelyi, T.; Wilbrandt, Robert; Zwier, Jurriaan M.; Brouwer, Albert M.; Buma, Wybren Jan.

In: Journal of Physical Chemistry A, Vol. 104, No. 9, 09.03.2000, p. 1834-1841.

Research output: Contribution to journalArticle

Balakrishnan, G, Keszthelyi, T, Wilbrandt, R, Zwier, JM, Brouwer, AM & Buma, WJ 2000, 'The radical cation and lowest Rydberg states of 1,4-diaza[2.2.2]bicyclooctane (DABCO)', Journal of Physical Chemistry A, vol. 104, no. 9, pp. 1834-1841.
Balakrishnan G, Keszthelyi T, Wilbrandt R, Zwier JM, Brouwer AM, Buma WJ. The radical cation and lowest Rydberg states of 1,4-diaza[2.2.2]bicyclooctane (DABCO). Journal of Physical Chemistry A. 2000 Mar 9;104(9):1834-1841.
Balakrishnan, Gurusamy ; Keszthelyi, T. ; Wilbrandt, Robert ; Zwier, Jurriaan M. ; Brouwer, Albert M. ; Buma, Wybren Jan. / The radical cation and lowest Rydberg states of 1,4-diaza[2.2.2]bicyclooctane (DABCO). In: Journal of Physical Chemistry A. 2000 ; Vol. 104, No. 9. pp. 1834-1841.
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