Water Clusters: Towards an Understanding Based on First Principles of Their Static and Dynamic Properties

Ugalde, Jesús M.; Alkorta, Ibón; Elguero, José

doi:10.1002/(sici)1521-3773(20000218)39:4<717::aid-anie717>3.0.co;2-e

Cited by 240 publications

(113 citation statements)

References 36 publications

(48 reference statements)

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“…͑6͒ is extended to all pair of coupled i-j orbitals depicted in Fig. 3 with the exception of the deepest 1a 1g and 29,47 This feature is particularly important in strong HBs of the type covered by this study. 48 One representative model is the three-center-four-electron ͑3c-4e͒ one originally introduced by Pimentel and Rundle 27 to explain bonding in hypervalent molecules.…”

Section: Analysis Of Thementioning

confidence: 76%

Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

García‐Fernández

García-Canales

Garcı́a-Lastra

et al. 2008

The Journal of Chemical Physics

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The microscopic origin and quantum effects of the low barrier hydrogen bond ͑LBHB͒ in the proton-bound ammonia dimer cation N 2 H 7 + were studied by means of ab initio and density-functional theory ͑DFT͒ methods. These results were analyzed in the framework of vibronic theory and compared to those obtained for the Zundel cation H 5 O 2 + . All geometry optimizations carried out using wavefunction-based methods ͓Hartree-Fock, second and fourth order Möller-Plesset theory ͑MP2 and MP4͒, and quadratic configuration interaction with singles and doubles excitations ͑QCISD͔͒ lead to an asymmetrical H 3 N-H +¯N H 3 conformation ͑C 3v symmetry͒ with a small energy barrier ͑1.26 kcal/ mol in MP4 and QCISD calculations͒ between both equivalent minima. The value of this barrier is underestimated in DFT calculations particularly at the local density approximation level where geometry optimization leads to a symmetric H 3 N¯H +¯N H 3 structure ͑D 3d point group͒. The instability of the symmetric D 3d structure is shown to originate from the pseudo-Jahn-Teller mixing of the electronic 1 A 1g ground state with five low lying excited states of A 2u symmetry through the asymmetric ␣ 2u vibrational mode. A molecular orbital study of the pseudo-Jahn-Teller coupling has allowed us to discuss the origin of the proton displacement and the LBHB formation in terms of the polarization of the NH 3 molecules and the transfer of electronic charge between the proton and the NH 3 units ͑rebonding͒. The parallel study of the H 5 O 2 + cation, which presents a symmetric single-well structure, allows us to analyze why these similar molecules behave differently with respect to proton transfer. From the vibronic analysis, a unified view of the Rudle-Pimentel three-center four-electron and charge transfer models of LBHBs is given. Finally, the large difference in the N-N distance in the D 3d and C 3v configurations of N 2 H 7 + indicates a large anharmonic coupling between ␣ 2u -␣ 1g modes along the proton-transfer dynamics. This issue was explored by solving numerically the vibrational Schrödinger equation corresponding to the bidimensional E͓Q͑␣ 2u ͒ , Q͑␣ 1g ͔͒ energy surface calculated at the MP4 / 6-311+ + G ** level of theory.

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Section: Analysis Of Thementioning

confidence: 76%

Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

García‐Fernández

García-Canales

Garcı́a-Lastra

et al. 2008

The Journal of Chemical Physics

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“…Some of the recent reviews on the subject can be found elsewhere. [2][3][4] The water dimer, the smallest water cluster which constitutes the fundamental step in the study of water clusters, has been studied in great detail experimentally [5][6][7][8][9][10][11] as well as theoretically. [12][13][14][15][16][17][18][19][20][21][22][23][24][25] It has been established that the most stable structure of a water dimer is of the C s symmetry and that it has a single hydrogen bond with a strength of 5.5 ( 0.7 kcal/ mol.…”

Section: Introductionmentioning

confidence: 99%

“…In this case, the "free" hydrogen atoms alternate in their arrangement above and below the plane of the O-O-O-O ring. Infrared (IR) spectra of benzene-(H 2 O) 4 11 and VRT spectra of (D 2 O) 4 42 and (H 2 O) 4 43 showed an equilibrium structure with S 4 symmetry having the concerted flipping motions of the free H atoms for the tetramer. Pentagonal rings of water molecules appear to be ubiquitous in nature, for example, in clathrate hydrates and in the solvation of hydrophobic groups of small molecules as well as in proteins and in DNA molecules.…”

Section: Introductionmentioning

confidence: 99%

Structure and Stability of Water Clusters (H₂O)_n, n = 8−20: An Ab Initio Investigation

Maheshwary¹,

Patel²,

et al. 2001

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Extensive ab initio calculations have been performed using the 6-31G(d,p) and 6-311++G(2d,2p) basis sets for several possible structures of water clusters (H 2 O) n , n ) 8-20. It is found that the most stable geometries arise from a fusion of tetrameric or pentameric rings. As a result, (H 2 O) n , n ) 8, 12, 16, and 20, are found to be cuboids, while (H 2 O) 10 and (H 2 O) 15 are fused pentameric structures. For the other water clusters (n ) 9, 11, 13, 14, and 17-19) under investigation, the most stable geometries can be thought of as arising from either the cuboid or the fused pentamers or a combination thereof. The stability of some of the clusters, namely, n ) 8-16, has also been studied using density functional theory. An attempt has been made to estimate the basis set superposition error and zero-point energy correction for such clusters at the HartreeFock (HF) level using the 6-311++G(2d,2p) basis set. To ensure that a minimum on the potential-energy surface has been located, frequency calculations have been carried out at the HF level using the 6-31G(d,p) and 6-311++G(2d,2p) basis sets for some of the clusters. Molecular electrostatic potential topography mapping has been employed for understanding the reactivity as well as the binding patterns of some of the structurally interesting clusters.

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“…Hence, exploring the structural and binding properties of small water clusters are almost the first step of understanding the properties of bulk water. To this aim, several theoretical studies have been carried out to investigate the strength of the hydrogen bonds and their cooperativity [25,26]. Recently, Won and Aluru [27,28] showed that the BNNTs exhibit superior water-filling behaviors because of the comparatively hydrogen bonding interactions between the nitrogen atoms of the BNNT and the water molecules.…”

Section: Introductionmentioning

confidence: 99%

A computational study of water adsorption on boron nitride nanotube

Beheshtian¹,

Behzadi²,

Esrafili³

et al. 2010

Struct Chem

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The effect of water molecule adsorption on the surface of (5,0) zigzag boron nitride nanotube was studied by density functional theory calculations. Geometrical optimizations were carried out at the B3LYP/6-31?G* level of theory. Six different configurations of water molecule(s) adsorption process including monomer (1WB and 1WN), dimer (2WB, 2WNN, and 2WBN), and trimer (3WB) clusters were obtained. The strengths of interactions were analyzed by the equilibrium geometries, binding energies, and charge transfer. The natural bonding analysis was also performed to investigate electronic properties. The results reveal that the adsorption of water is more favorable as the water cluster size increases.

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Water Clusters: Towards an Understanding Based on First Principles of Their Static and Dynamic Properties

Cited by 240 publications

References 36 publications

Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

Structure and Stability of Water Clusters (H₂O)_n, n = 8−20: An Ab Initio Investigation

A computational study of water adsorption on boron nitride nanotube

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Water Clusters: Towards an Understanding Based on First Principles of Their Static and Dynamic Properties

Cited by 240 publications

References 36 publications

Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

Structure and Stability of Water Clusters (H2O)n, n = 8−20: An Ab Initio Investigation

A computational study of water adsorption on boron nitride nanotube

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Product

Resources

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Structure and Stability of Water Clusters (H₂O)_n, n = 8−20: An Ab Initio Investigation