Electronic excitation in the benzonitrile dimer: The intermolecular structure in the S0 and S1 state determined by rotationally resolved electronic spectroscopy

Schmitt, Michaël; Böhm, Marcel; Ratzer, Christian; Siegert, Swen; Beek, Marloes Van; Meerts, W. Leo

doi:10.1016/j.molstruc.2006.02.036

Cited by 22 publications

(40 citation statements)

References 25 publications

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“…The only exception is that the SCS-CC2 calculation predicts a decrease of the center-of-mass intermolecular distance R AB,COM of −0.3 pm, significantly smaller than the −2.8 and −2 pm analyzed by Schmitt and coworkers. 18,19 The small change of intermolecular distance is in agreement with the fact that the intermolecular vibronic excitations in the (BN) 2 spectrum are very weak. Table 4 predicts that the structure change between the S 0 and S 1 state (BN) 2 are almost entirely restricted to one of the BN monomers, while the other retains the structure of the ground state.…”

Section: Excitation Transfer Ratessupporting

confidence: 80%

“…37 Schmitt et al determined the rotational constants of (BN) 2 in its S 0 and S 1 (actually S 2 , see below) states by high-resolution LIF spectroscopy. 18 The S 0 state was determined to be C 2h symmetric, in agreement with earlier MP2/6-31G(d,p) ab initio calculations. 18,38 Schmitt et al found the excited state structure to be asymmetric and proposed that the excitation is localized on one of the BN monomers, supported by CIS calculations which also predict a nonsymmetric structure.…”

Section: Introductionsupporting

confidence: 81%

“…As outlined in the Introduction, the experimentally observed geometric asymmetries of excited-state (benzoic acid) 2 and (benzonitrile) 2 led several groups to postulate the localization of the excitonic excitation on one of the monomers. 13,14,18,19,25,26 In section 4.1 we showed that a single 0 0 0 band is observed in inversion-symmetric (C i or C 2h ) homodimers and that two electronic origins are only observed upon symmetry breaking such as isotopic substitution. In sections 4.2 and 4.3 we have discussed the topic of excitonic wave function localization vs delocalization.…”

Section: Excitation Transfer Ratesmentioning

confidence: 84%

“…Table 4 summarizes the changes of selected geometrical parameters between the S 0 and S 1 states, as derived experimentally by Schmitt et al, 18 Borst et al, 19 and as calculated with the SCS-CC2/aug-cc-pVDZ method. The calculated geometry changes are in good agreement with experiment.…”

Section: Excitation Transfer Ratesmentioning

confidence: 99%

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

2014

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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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Section: Excitation Transfer Ratessupporting

confidence: 80%

Section: Introductionsupporting

confidence: 81%

Section: Excitation Transfer Ratesmentioning

confidence: 84%

Section: Excitation Transfer Ratesmentioning

confidence: 99%

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

2014

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“…14,15 Cyanobenzene forms a planar dimer with C 2h structure with two C-H¯N hydrogen bonds a͒ Electronic mail: martina.havenith@ruhr-uni-bochum.de. THE JOURNAL OF CHEMICAL PHYSICS 129, 174311 ͑2008͒ between the monomers.…”

Section: Introduction: Tcnb and Its Dimermentioning

confidence: 99%

High resolution infrared spectroscopy of the asymmetric C–H stretch of 1,2,4,5-tetracyanobenzene (TCNB) and (TCNB)2 in superfluid helium nanodroplets

Gutberlet

Birer

Poerschke

et al. 2008

The Journal of Chemical Physics

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We report the observation of the C-H stretch vibration of 1,2,4,5-tetracyanobenzene (TCNB) and (TCNB)(2) embedded in superfluid helium droplets. The asymmetric C-H stretch of TCNB was observed at 3053.488(3) cm(-1). The corresponding band of the (TCNB)(2) is slightly blueshifted and was observed at 3054.651(2) cm(-1). The intensity of the IR band is increased compared to the monomer absorption. Based on a comparison of our experimental results with predicted IR bands, we conclude that (TCNB)(2) is formed in a C(2h) structure in the droplet.

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Rotationally Resolved Electronic Spectroscopy and Automatic Assignment Techniques using Evolutionary Algorithms

Schmitt

Meerts

2011

Handbook of High‐resolution Spectroscopy

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The usefulness of an evolutionary algorithm (EA)‐based approach to the automated evaluation of molecular parameters from various kinds of spectra is shown. The applicability of the method ranges from rotationally resolved electronic spectroscopy of large molecules to nuclear magnetic resonance (NMR) spectroscopy of molecules, which are partially oriented in an anisotropic liquid‐crystalline environment. The application of both the genetic algorithm (GA) and the evolution strategy algorithm (ES) approaches for the assignment of complex spectra and the necessity of fitting meta parameters, which are not related to the parameters of the model describing the spectra are discussed. Examples for the possible applications comprise rovibronic spectra of various aromatic water clusters, rovibronic spectra of large hetero‐ and homo‐dimers, rovibrational spectra of the NH stretching vibrations in different tautomers of benzotriazole, and the NMR spectrum of p ‐bromo‐biphenyl dissolved in a nematic crystal.

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Electronic excitation in the benzonitrile dimer: The intermolecular structure in the S0 and S1 state determined by rotationally resolved electronic spectroscopy

Cited by 22 publications

References 25 publications

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

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

High resolution infrared spectroscopy of the asymmetric C–H stretch of 1,2,4,5-tetracyanobenzene (TCNB) and (TCNB)2 in superfluid helium nanodroplets

Rotationally Resolved Electronic Spectroscopy and Automatic Assignment Techniques using Evolutionary Algorithms

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