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Title: Quantum calculations of the IR spectrum of liquid water using ab initio and model potential and dipole moment surfaces and comparison with experiment

Abstract

The calculation and characterization of the IR spectrum of liquid water have remained a challenge for theory. In this paper, we address this challenge using a combination of ab initio approaches, namely, a quantum treatment of IR spectrum using the ab initio WHBB water potential energy surface and a refined ab initio dipole moment surface. The quantum treatment is based on the embedded local monomer method, in which the three intramolecular modes of each embedded H{sub 2}O monomer are fully coupled and also coupled singly to each of six intermolecular modes. The new dipole moment surface consists of a previous spectroscopically accurate 1-body dipole moment surface and a newly fitted ab initio intrinsic 2-body dipole moment. A detailed analysis of the new dipole moment surface in terms of the coordinate dependence of the effective atomic charges is done along with tests of it for the water dimer and prism hexamer double-harmonic spectra against direct ab initio calculations. The liquid configurations are taken from previous molecular dynamics calculations of Skinner and co-workers, using the TIP4P plus E3B rigid monomer water potential. The IR spectrum of water at 300 K in the range of 0–4000 cm{sup −1} is calculated and compared withmore » experiment, using the ab initio WHBB potential and new ab initio dipole moment, the q-TIP4P/F potential, which has a fixed-charged description of the dipole moment, and the TTM3-F potential and dipole moment surfaces. The newly calculated ab initio spectrum is in very good agreement with experiment throughout the above spectral range, both in band positions and intensities. This contrasts to results with the other potentials and dipole moments, especially the fixed-charge q-TIP4P/F model, which gives unrealistic intensities. The calculated ab initio spectrum is analyzed by examining the contribution of various transitions to each band.« less

Authors:
; ;  [1]
  1. Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States)
Publication Date:
OSTI Identifier:
22415803
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 19; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPARATIVE EVALUATIONS; DIMERS; DIPOLE MOMENTS; INFRARED SPECTRA; LIQUIDS; MOLECULAR DYNAMICS METHOD; MONOMERS; POTENTIAL ENERGY; POTENTIALS; PRISMS; SURFACES; WATER

Citation Formats

Liu, Hanchao, Wang, Yimin, and Bowman, Joel M. Quantum calculations of the IR spectrum of liquid water using ab initio and model potential and dipole moment surfaces and comparison with experiment. United States: N. p., 2015. Web. doi:10.1063/1.4921045.
Liu, Hanchao, Wang, Yimin, & Bowman, Joel M. Quantum calculations of the IR spectrum of liquid water using ab initio and model potential and dipole moment surfaces and comparison with experiment. United States. doi:10.1063/1.4921045.
Liu, Hanchao, Wang, Yimin, and Bowman, Joel M. 2015. "Quantum calculations of the IR spectrum of liquid water using ab initio and model potential and dipole moment surfaces and comparison with experiment". United States. doi:10.1063/1.4921045.
@article{osti_22415803,
title = {Quantum calculations of the IR spectrum of liquid water using ab initio and model potential and dipole moment surfaces and comparison with experiment},
author = {Liu, Hanchao and Wang, Yimin and Bowman, Joel M.},
abstractNote = {The calculation and characterization of the IR spectrum of liquid water have remained a challenge for theory. In this paper, we address this challenge using a combination of ab initio approaches, namely, a quantum treatment of IR spectrum using the ab initio WHBB water potential energy surface and a refined ab initio dipole moment surface. The quantum treatment is based on the embedded local monomer method, in which the three intramolecular modes of each embedded H{sub 2}O monomer are fully coupled and also coupled singly to each of six intermolecular modes. The new dipole moment surface consists of a previous spectroscopically accurate 1-body dipole moment surface and a newly fitted ab initio intrinsic 2-body dipole moment. A detailed analysis of the new dipole moment surface in terms of the coordinate dependence of the effective atomic charges is done along with tests of it for the water dimer and prism hexamer double-harmonic spectra against direct ab initio calculations. The liquid configurations are taken from previous molecular dynamics calculations of Skinner and co-workers, using the TIP4P plus E3B rigid monomer water potential. The IR spectrum of water at 300 K in the range of 0–4000 cm{sup −1} is calculated and compared with experiment, using the ab initio WHBB potential and new ab initio dipole moment, the q-TIP4P/F potential, which has a fixed-charged description of the dipole moment, and the TTM3-F potential and dipole moment surfaces. The newly calculated ab initio spectrum is in very good agreement with experiment throughout the above spectral range, both in band positions and intensities. This contrasts to results with the other potentials and dipole moments, especially the fixed-charge q-TIP4P/F model, which gives unrealistic intensities. The calculated ab initio spectrum is analyzed by examining the contribution of various transitions to each band.},
doi = {10.1063/1.4921045},
journal = {Journal of Chemical Physics},
number = 19,
volume = 142,
place = {United States},
year = 2015,
month = 5
}
  • A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO{sup +}(H{sub 2}O) cluster is reported. The PES is based on fitting of roughly 32 000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) using the MULTIMODEmore » program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO{sup +}(H{sub 2}O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water “antisymmetric” stretching mode with the low-frequency intermolecular modes results in intensity borrowing.« less
  • Potential energy and dipole moment surfaces for the water molecule have been generated by multireference singles-and-doubles configuration interaction calculations using a large basis set of the averaged-atomic-natural-orbital type and a six-orbital-six-electron complete-active-space reference space. The surfaces are suitable for modeling vibrational transitions up to about 11000cm{sup {minus}1} above the ground state. A truncated singular-value decomposition method has been used to fit the surfaces. This fitting method is numerically stable and is a useful tool for examining the effectiveness of various fitting function forms in reproducing the calculated surface points and in extrapolating beyond these points. The fitted surfaces have beenmore » used for variational calculations of the 30 lowest band origins and the corresponding band intensities for transitions from the ground vibrational state. With a few exceptions, the results compare well with other calculations and with experimental data. {copyright} {ital 1997 American Institute of Physics.}« less
  • The rotational spectra of six isotopic species of trans-difluoroethylene ozonide (trans-3,5-difluoro-1,2,4-trioxolane) were assigned. These included the parent species, the single- and double-substituted deuterium species, the double /sup 18/O/sub p/, the triple /sup 18/O, and and /sup 13/C species. The spectrum consisted of b-type transitions with a 10:6 intensity alternation. The electric dipole moment was determined from Stark effect measurements to be ..mu../sub b/ = 0.994 (5) D. These results support an average structure having an O/sub p/-O/sub p/ twist ring conformation with C/sub 2/ symmetry and diaxial fluorine substituents. The shortening of the C-O/sub p/ bonds (1.368 A) relative tomore » the C-O/sub c/ bonds (1.401 A) is very apparent in this member of the fluoroozonide series. Ab initio calculations were performed at the HG/6-31G/sup */ level and analyzed in terms of electron density distributions. Experimental and theoretical results are rationalized in terms of anomeric interactions with the peroxy oxygen atoms.« less
  • In this work we examine the consequences of incorporating the ab-initio derived monomer potential energy surface and non-linear dipole surface of Partridge and Schwenke [J. Chem. Phys. 106, 4618 (1997)] into the previously developed TTM2-R model of Burnham et al. [J. Chem. Phys. xx. yyyy (2001)] in order to develop a new, all-atom polarizable, flexible model for water (TTM2-F). We found that the use of the non-linear dipole surface is essential in modeling the change in the internal geometry of interacting water molecules and, in particular, the increase in the internal H-O-H bend angle with cluster size. This is themore » first demonstration of a flexible model which shows an increase in the bending angle in clusters. An explanation for this behavior is presented using the concept of geometric polarizabilities . The model furthermore reproduces the n=2-6 cluster binding energies to within an RMS deviation of 0.05 kcal/mol per hydrogen bond with respect to the MP2 complete basis set estimates.« less
  • Accurate {ital ab initio} multireference configuration interaction (CI) calculations with large correlation-consistent basis sets are performed for HOCl. After extrapolation to the complete basis set limit, the {ital ab initio} data are precisely fit to give a semiglobal three-dimensional potential energy surface to describe HOCl{r_arrow}Cl+OH from high overtone excitation of the OH-stretch. The average absolute deviation between the {ital ab initio} and fitted energies is 4.2thinspcm{sup {minus}1} for energies up to 60 kcal/mol relative to the HOCl minimum. Vibrational energies of HOCl including the six overtones of the OH-stretch are computed using a vibrational-Cl method on the fitted potential andmore » also on a slightly adjusted potential. Near-spectroscopic accuracy is obtained using the adjusted potential; the average absolute deviation between theory and experiment for 19 experimentally reported states is 4.8thinspcm{sup {minus}1}. Very good agreement with experiment is also obtained for numerous rotational energies for the ground vibrational state, the ClO-stretch fundamental, and the fifth overtone of the OH-stretch. {copyright} {ital 1998 American Institute of Physics.}« less