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Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO3(HNO3)m(H2O)n

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Heine,  Nadja
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Schubert,  Franziska
Theory, Fritz Haber Institute, Max Planck Society;

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Brieger,  Claudia
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Asmis,  Knut R.
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig;

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Citation

Heine, N., Yacovitch, T. I., Schubert, F., Brieger, C., Neumark, D. M., & Asmis, K. R. (2014). Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO3(HNO3)m(H2O)n. The Journal of Physical Chemistry A, 118(35), 7613-7622. doi:10.1021/jp412222q.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0018-6948-8
Abstract
Infrared multiple photon dissociation (IRMPD) spectra of NO3¯ (HNO3)m(H2O)n(H2)z with m = 1-3, up to n = 8 and z ≥ 1 are measured in the fingerprint region (550 – 1800 cm-1), directly probing the NO–stretching modes, as well as bending and other lower frequency modes. The assignment of the spectra is aided by electronic structure calculations. The IRMPD spectrum of the m = 1, n = 0 cluster is distinctly different from all the other measured spectra as a result of strong hydrogen bonding, leading to an equally shared proton in-between two nitrate moieties (NO3¯∙∙∙H+∙∙∙NO3¯). It exhibits a strong absorption at 877 cm-1 and lacks the characteristic NO2-antisymmetric stretch/NOH-bending mode absorption close to 1650 cm-1. Addition of at least one more nitric acid molecule or two more water molecules weakens the hydrogen bond network, breaking the symmetry of this arrangement and leading to localization of the proton near one of the nitrate cores, effectively forming HNO3 hydrogen-bonded to NO3¯. Not all IR active modes are observed in the IRMPD spectra of the bare nitrate-nitric acid clusters. Addition of a water or a hydrogen molecule lowers the dissociation limit of the complexes and relaxes (H2O) or lifts (H2) this IRMPD transparency.