Excitonic Splitting, Delocalization, and Vibronic Quenching in the Benzonitrile Dimer

Balmer, Franziska A.; Ottiger, Philipp; Leutwyler, Samuel (2014). Excitonic Splitting, Delocalization, and Vibronic Quenching in the Benzonitrile Dimer. Journal of physical chemistry. A, 118(47), pp. 11253-11261. American Chemical Society 10.1021/jp509626b

[img] Text
jp509626b.pdf - Published Version
Restricted to registered users only
Available under License Publisher holds Copyright.

Download (1MB) | Request a copy

The excitonic S1/S2 state splitting and the localization/delocalization of the S1 and S2 electronic states are investigated in the benzonitrile dimer (BN)2 and its 13C and d5 isotopomers by mass-resolved two-color resonant two-photon ionization spectroscopy in a supersonic jet, complemented by calculations. The doubly hydrogen-bonded (BN-h5)2 and (BN-d5)2 dimers are C2h symmetric with equivalent BN moieties. Only the S0 → S2 electronic origin is observed, while the S0 → S1 excitonic component is electric-dipole forbidden. A single 12C/13C or 5-fold h5/d5 isotopic substitution reduce the dimer symmetry to Cs, so that the heteroisotopic dimers (BN)2-(h5 – h513C), (BN)2-(h5 – d5), and (BN)2-(h5 – h513C) exhibit both S0 → S1 and S0 → S2 origins. Isotope-dependent contributions Δiso to the excitonic splittings arise from the changes of the BN monomer zero-point vibrational energies; these range from Δiso(12C/13C) = 3.3 cm–1 to Δiso(h5/d5) = 155.6 cm–1. The analysis of the experimental S1/S2 splittings of six different isotopomeric dimers yields the S1/S2 exciton splitting Δexc = 2.1 ± 0.1 cm–1. Since Δiso(h5/d5) ≫ Δexc and Δiso(12C/13C) > Δexc, complete and near-complete exciton localization occurs upon 12C/13C and h5/d5 substitutions, respectively, as diagnosed by the relative S0 → S1 and S0 → S2 origin band intensities. The S1/S2 electronic energy gap of (BN)2 calculated by the spin-component scaled approximate second-order coupled-cluster (SCS-CC2) method is Δelcalc = 10 cm–1. This electronic splitting is reduced by the vibronic quenching factor Γ. The vibronically quenched exciton splitting Δelcalc·Γ = Δvibroncalc = 2.13 cm–1 is in excellent agreement with the observed splitting Δexc = 2.1 cm–1. The excitonic splittings can be converted to semiclassical exciton hopping times; the shortest hopping time is 8 ps for the homodimer (BN-h5)2, the longest is 600 ps for the (BN)2(h5 – d5) heterodimer.

Item Type:

Journal Article (Original Article)


08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Ottiger, Philipp and Leutwyler, Samuel


500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
500 Science




American Chemical Society




Beatrice Niederhauser

Date Deposited:

25 Mar 2015 14:33

Last Modified:

25 Aug 2015 10:24

Publisher DOI:






Actions (login required)

Edit item Edit item
Provide Feedback