DFT study of polarizabilities and dipole moments of water clusters

Abstract

Density functional theory (DFT) calculations with different exchangecorrelation functionals, Becke's three-parameter exchange functional and the gradientcorrected functional of Lee, Yang, and Paar (B3LYP) and Becke's three-parameter functional with Perdew-Wang correlational functional (B3PW91), are performed to study the dielectric properties of small and medium-sized water clusters. For these Hbonded systems, we optimize the geometries and compute the dipole moments and polarizabilities using a supermolecule approach. The corresponding properties of the individual water molecules in the clusters are extracted from the molecular properties using the Hirshfeld expansion of the electronic density. Calculations at Hartree-Fock and second-order Møller-Plesset (MP2) levels are also presented for a comparison with the DFT results. The dependence of the dielectric properties on the cluster structure and size is given for both clusters and individual molecules and is compared with the available experimental data. The intermolecular interactions and their influences on the dielectric properties are discussed. The current results could serve to improve existing polarizable force fields for water.

Dynamic polarizability, Cauchy moments, and the optical absorption spectrum of liquid water: A sequential molecular dynamics/quantum mechanical approach

“…8 The strong interest on this subject motivated several theoretical studies on the electronic properties of water 14 with emphasis on the calculation of electronic excitations and molecular polarizabilities. [15][16][17][18][19][20] Recently, some theoretical studies were dedicated to the study of the optical absorption and dielectric properties of liquid water. [21][22][23][24] In spite of the relative success of these theoretical studies some important questions persist.…”

Electric Dipole Moments of Nitric Acid-Water Complexes Measured by Cluster Beam Deflection

“…For water α electronic was taken from the calculations in Ref. [15], and for the nitric acid molecule the estimate given in Ref. [16] was used.…”

A quantitative analysis of intramolecular charge transfer contribution to polarizability responses in donor-π-acceptor molecules

“…Different from previous studies [15][16][17][18][19] on the interatomic or intermolecular charge transfer and their influences on cluster polarization, we here focus on the intramolecular charge transfer and its influences on molecular polarization. The polarizability partitioning scheme is slightly modified to match the specificity of molecular systems.…”

“…Stone [8,9] developed a general theory of distributed polarizability based on distributed multipole analysis. Ángyán et al [10,11] proposed a scheme to topologically partition electric properties by using Bader's theory of atoms in molecules (AIM) and applied it into the study of intermolecular interaction energies and distributed polarizabilities of homomolecular dimers such as H 2 O and CO. Based on Hirshfeld population analysis [12][13][14], we have reported an alternative polarizability partitioning scheme in our previous studies [15][16][17][18][19]. The total polarizability of atomic or molecular clusters is decomposed into local and charge-transfer parts.…”