Infrared Spectroscopy of H3O+: The ν1 Fundamental Band

Large-amplitude quantum mechanics in polyatomic hydrides. II. A particle-on-a-sphere model for XHn (n=4,5)

“…In systems with few degrees of freedom, the exact quantum nuclear dynamics can be solved in full dimensionality, as in the wellstudied triatomic systems (3D) such as H 2 O [1][2][3][4] . Tetraatomic molecules require 6D and are significantly more challenging, but have been successfully tackled in a number of floppy systems, most notably the large-amplitude motion and tunneling inversion in ammonia [5][6][7][8][9][10][11][12] (NH 3 ) and hydronium ion [13][14][15][16][17][18][19][20] (H 3 O + ). There have also been impressive advances in tetraatomic van der Waals complexes, such as the landmark 6D studies of HF and HCl dimers [21][22][23][24] , as well as reduced-dimensionality extensions to H 2 O dimer [25][26][27][28] using sixdimensional (6D) intermolecular coordinates with semirigid H 2 O molecules.…”

Peculiarities of formation of hydroxonium ion and its small clusters

“…However, selectivity of the intermolecular bonding involving hydroxonium ion and its effect on the cluster nuclearity have remained the open issues so far. Furthermore, the reported lengths of hydrogen bonds and ОН groups in the mentioned clusters have been uncertain; potential energy surfaces of hydroxonium ion formation and decomposition have not been analyzed; assignments of vibrations of O-H bond of DOI: 10.1134/S1070363215050011 hydroxonium ion and the protonated Н + (H 2 O) n (n = 5-8) systems to the vibrational frequencies have been ambiguous [24]; IR spectroscopy data for hydroxonium ion has been contradictory [26][27][28][29][30][31][32][33][34][35][36][37][38].…”

“…Geometry of hydroxonium ion clusters with several (up to 10) water molecules in gas and condensed phase has been studied in detail as well [20][21][22][23][24][25][26][27][28][29][30]. However, selectivity of the intermolecular bonding involving hydroxonium ion and its effect on the cluster nuclearity have remained the open issues so far.…”

“…Vibrational and electronic spectra were simulated using the B3LYP functional and the 6-311G** basis allowing the best coincidence between the experimental and the simulated О-Н dissociation energy and geometry parameters of Н 2 О molecule [18,[25][26][27][28]. On top of that, the B3LYP and B3PW91 functionals could adequately reproduce vibrational frequencies of the H 3 O + ion and its clusters with water molecules [15,16,23,[31][32][33][34][35].…”

“…The optimized parameters of equilibrium states of the Zundel [25,30] and Eigen [21,30] hydroxonium ions, water molecule [18,[25][26][27][28], and the H 3 O + -n(Н 2 O) (n = 2, 3) complexes [18,23,29,30] obtained by us using the DFT method with different functionals (Tables 1 and 2) coincided with the results of spectral [16,42], resonance, and X-ray diffraction measurements as well as with the simulation data [16, 18-20, 25, 27-29, 33, 35, 36]. Cross-sections of potential energy surfaces of the…”