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Updated: Apr 21, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Excitonic splitting, delocalization, and vibronic quenching in the benzonitrile dimer
Franziska A Balmer1, Philipp Ottiger, Samuel Leutwyler
1Department of Chemistry and Biochemistry, University of Bern , Freiestrasse 3, CH-3012 Bern, Switzerland.
Abstract:
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 (13)C 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 (12)C/(13)C or 5-fold h5/d5 isotopic substitution reduce the dimer symmetry to Cs, so that the heteroisotopic dimers (BN)2-(h5 – h5(13)C), (BN)2-(h5 – d5), and (BN)2-(h5 – h5(13)C) 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((12)C/(13)C) = 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((12)C/(13)C) > Δexc, complete and near-complete exciton localization occurs upon (12)C/(13)C 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 Δel(calc) = 10 cm(–1). This electronic splitting is reduced by the vibronic quenching factor Γ. The vibronically quenched exciton splitting Δel(calc)·Γ = Δvibron(calc) = 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.
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