Electronic and vibrational spectra of the low-lying pisigma* state of 4-dimethylaminobenzonitrile: comparison of theoretical predictions with experiment

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DOIResolve DOI: http://doi.org/10.1063/1.1889431
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TypeArticle
Journal titleThe Journal Of Chemical Physics
ISSN00219606
Volume122
Issue11
Pages111103–; # of pages: 1
AbstractComparison of the TD-BP86cc-pVDZ electronic excitation energies and the CIScc-pVDZ vibrational frequencies of 4-dimethylaminobenzonitrile with the available experimental data indicates that the picosecond transient absorption at about 700 nm, and the excited-state vibration of frequency 1467 cm(-1), belong to the lowest-energy pisigma(CN) (*) state of bent geometry (CCN bond angle of about 120 degrees and a large CN bond distance). Consistent with these assignments, the 1467 cm(-1) Raman band, attributed to the CN stretch, exhibits a large resonance enhancement of intensity when the probe (Raman excitation) wavelength is set to the spectral region of the pisigma(*)<--pisigma(*) absorption. The result corroborates the occurrence of an ultrafast state switch from the initially excited (1)pipi(*) (L(b)) state to the (1)pisigma(*) state of lower energy.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedYes
Identifier10012680
NPARC number12327727
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Record identifier0a71f75b-5ac5-4d94-b4b8-e5db433bfd96
Record created2009-09-10
Record modified2017-03-23
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