Infrared Spectra of Deprotonated Dicarboxylic Acids: IRMPD Spectroscopy and Empirical Valence‐Bond Modeling

Florian Thaunay (1) , Florent Calvo (2) , Edith Nicol (3) , Gilles Ohanessian (3) , Carine Clavaguéra (4)

1 LCM - Laboratoire de chimie moléculaire
2 LIPhy - Laboratoire Interdisciplinaire de Physique [Saint Martin d’Hères]
3 DCMR - Laboratoire des mécanismes réactionnels
4 LCPO - Laboratoire de Chimie Physique D'Orsay

Experimental infrared multiple-photon dissociation (IRMPD) spectra recorded for a series of deprotonated dicarboxylic acids, HO 2 (CH 2) n CO À 2 (n = 2-4), are interpreted using a variety of computational methods. The broad bands centered near 1600 cm À 1 can be reproduced neither by static vibrational calculations based on quantum chemistry nor by a dynamical description of individual structures using the many-body polar-izable AMOEBA force field, strongly suggesting that these molecules experience dynamical proton sharing between the two carboxylic ends. To confirm this assumption, AMOEBA was combined with a two-state empirical valence-bond (EVB) model to allow for proton transfer in classical molecular dynamics simulations. Upon suitable parametrization based on ab initio reference data, the EVB-AMOEBA model satisfactorily reproduces the experimental infrared spectra, and the finite temperature dynamics reveals a significant amount of proton sharing in such systems.

Domaines: Chimie théorique et/ou physique

Florian Thaunay, Florent Calvo, Edith Nicol, Gilles Ohanessian, Carine Clavaguéra. Infrared Spectra of Deprotonated Dicarboxylic Acids: IRMPD Spectroscopy and Empirical Valence‐Bond Modeling. ChemPhysChem, 2019, 20 (6), pp.803-814. ⟨10.1002/cphc.201800947⟩. ⟨hal-02161622⟩