Vibrational and electronic photodissociation spectra of mass-selected protonated benzaldehyde-(water)n clusters, [BZ-(H2O)n]H+ with n ≤ 5, are analyzed by quantum chemical calculations to determine the protonation site in the ground electronic state (S0) and ππ* excited state (S1) as a function of microhydration. IR spectra of [BZ-(H2O)n]H+ with n ≤ 2 are consistent with BZH+-(H2O)n type structures, in which the excess proton is localized on benzaldehyde. IR spectra of clusters with n ≥ 3 are assigned to structures, in which the excess proton is located on the (H2O)n solvent moiety, BZ-(H2O)nH+. Quantum chemical calculations at the B3LYP, MP2, and ri-CC2 levels support the conclusion of proton transfer from BZH+ to the solvent moiety in the S0 state for hydration sizes larger than the critical value nc = 3. The vibronic spectrum of the S1 ← S0 transition (ππ*) of the n = 1 cluster is consistent with a cis-BZH+-H2O structure in both electronic states. The large blueshift of the S1 origin by 2106 cm−1 upon hydration with a single H2O ligand indicates that the proton affinity of BZ is substantially increased upon S1 excitation, thus strongly destabilizing the hydrogen bond to the solvent. The adiabatic S1 excitation energy and vibronic structure calculated at the ri-CC2/aug-cc-pVDZ level agrees well with the measured spectrum, supporting the notion of a cis-BZH+-H2O geometry. The doubly hydrated species, cis-BZH+-(H2O)2, does not absorb in the spectral range of 23 000–27 400 cm−1, because of the additional large blueshift of the ππ* transition upon attachment of the second H2O molecule. Calculations predict roughly linear and large incremental blueshifts for the ππ* transition in [BZ-(H2O)n]H+ as a function of n. In the size range n ≥ 3, the calculations predict a proton transfer from the (H2O)nH+ solvent back to the BZ solute upon electronic ππ* excitation.
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28 March 2014
Research Article|
March 31 2014
Electronic and vibrational spectra of protonated benzaldehyde-water clusters, [BZ-(H2O)n≤5]H+: Evidence for ground-state proton transfer to solvent for n ≥ 3
Otto Dopfer;
Otto Dopfer
a)
1Institut für Optik und Atomare Physik,
Technische Universität Berlin
, Hardenbergstrasse 36, 10623 Berlin, Germany
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Alexander Patzer;
Alexander Patzer
1Institut für Optik und Atomare Physik,
Technische Universität Berlin
, Hardenbergstrasse 36, 10623 Berlin, Germany
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Shamik Chakraborty;
Shamik Chakraborty
1Institut für Optik und Atomare Physik,
Technische Universität Berlin
, Hardenbergstrasse 36, 10623 Berlin, Germany
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Ivan Alata;
Ivan Alata
2
Institut des Sciences Moleculaires d’Orsay
, UMR-CNRS 8214, and Centre Laser de l’Université Paris Sud/LUMAT FR 2764, Batiment 106, l’Université Paris Sud 11, 91405 Orsay Cedex, France
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Reza Omidyan;
Reza Omidyan
2
Institut des Sciences Moleculaires d’Orsay
, UMR-CNRS 8214, and Centre Laser de l’Université Paris Sud/LUMAT FR 2764, Batiment 106, l’Université Paris Sud 11, 91405 Orsay Cedex, France
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Michel Broquier;
Michel Broquier
2
Institut des Sciences Moleculaires d’Orsay
, UMR-CNRS 8214, and Centre Laser de l’Université Paris Sud/LUMAT FR 2764, Batiment 106, l’Université Paris Sud 11, 91405 Orsay Cedex, France
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Claude Dedonder;
Claude Dedonder
3
Physique des Interactions Ioniques et Moléculaires
, UMR-CNRS 7345 Aix Marseille Université, Avenue Escadrille Normandie-Niémen, 13397 Marseille Cedex 20, France
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Christophe Jouvet
Christophe Jouvet
3
Physique des Interactions Ioniques et Moléculaires
, UMR-CNRS 7345 Aix Marseille Université, Avenue Escadrille Normandie-Niémen, 13397 Marseille Cedex 20, France
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]. Fax: (+49) 30-31423018.
J. Chem. Phys. 140, 124314 (2014)
Article history
Received:
February 17 2014
Accepted:
March 12 2014
Citation
Otto Dopfer, Alexander Patzer, Shamik Chakraborty, Ivan Alata, Reza Omidyan, Michel Broquier, Claude Dedonder, Christophe Jouvet; Electronic and vibrational spectra of protonated benzaldehyde-water clusters, [BZ-(H2O)n≤5]H+: Evidence for ground-state proton transfer to solvent for n ≥ 3. J. Chem. Phys. 28 March 2014; 140 (12): 124314. https://doi.org/10.1063/1.4869341
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