skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: An extended basis set ab initio study of Li+(H2O)n,n=1-6

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.467217· OSTI ID:1491727
 [1];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
+ Show Author Affiliations

We report that the structures, binding energies, and enthalpies of small molecular clusters incorporating a single lithium cation and up through six waters have been determined with extended Gaussian basis sets using Hartree–Fock and post-Hartree–Fock methods. The resulting properties are analyzed with respect to both basis set completeness and degree of correlation recovery, including core–core and core–valence effects. Although the lithium–water interaction is largely electrostatic in nature, small basis sets, lacking in polarization and near-valence diffuse functions, drastically overestimate the strength of the bond (by 20 kcal/mol or more) and underestimate the Li+...O distance by up to 0.1 Å. Their poor performance is attributable to inherent errors in describing the electric moments and polarizability of water and to large basis set superposition errors. Thus, the accuracy with which the fundamental lithium–water interaction could be modeled was primarily dependent on the quality of the Gaussian basis set and not upon the level of correlation recovery. Basis set enlargement and correlation effects both tend to reduce the strength of the Li+(H2O) bond, but produce corrections of opposite sign for the Li+...O bond length. Finally, although correlation effects play a minor role in describing the lithium–water interaction, as the size of the cluster increases and the number of waters involved in multiple hydrogen bonds grows, correlation recovery can become significant.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1491727
Report Number(s):
PNL-SA-23188
Journal Information:
Journal of Chemical Physics, Vol. 100, Issue 7; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 174 works
Citation information provided by
Web of Science

References (31)

Extensive theoretical studies of the hydrogen‐bonded complexes (H 2 O) 2 , (H 2 O) 2 H + , (HF) 2 , (HF) 2 H + , F 2 H − , and (NH 3 ) 2 journal February 1986
Ab initio studies of the water dimer using large basis sets: The structure and thermodynamic energies journal November 1992
Quadratic configuration interaction. A general technique for determining electron correlation energies journal November 1987
Theoretical study of the (H2O)6 cluster journal October 1993
Application of systematic sequences of wave functions to the water dimer journal April 1992
A theoretical study of Na(H 2 O) + n ( n =1–4) journal October 1991
Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals journal September 1969
Non-additivity in water-ion-water interactions journal December 1980
Two-dimensional, fully numerical molecular calculations: X. Hartree-fock results for He journal December 1985
Ab initio studies of cyclic water clusters (H 2 O) n , n =1–6. I. Optimal structures and vibrational spectra journal December 1993
Binding of lithium(1+) ion to Lewis bases in the gas phase. Reversals in methyl substituent effects for different reference acids journal January 1978
Partially deuterated water dimers: Microwave spectra and structure journal May 1980
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
On the CH bond dissociation energy of acetylene journal April 1990
Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements journal January 1980
The use of systematic sequences of wave functions for estimating the complete basis set, full configuration interaction limit in water journal May 1993
Study of the Structure of Molecular Complexes. I. Energy Surface of a Water Molecule in the Field of a Lithium Positive Ion journal August 1972
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Rotation‐Vibration Spectra of Deuterated Water Vapor journal June 1956
A complete basis set model chemistry. III. The complete basis set‐quadratic configuration interaction family of methods journal May 1991
Convergence to the basis‐set limit in ab initio calculations at the correlated level on the water dimer journal October 1992
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon journal January 1993
Comparison of theoretical methods for the determination of the Li+ Affinities of neutral and anionic first- and second-row bases journal March 1990
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors journal October 1970
Hydration of the alkali ions in the gas phase. Enthalpies and entropies of reactions M+(H2O)n-1 + H2O = M+(H2O)n journal April 1970
A molecular orbital study of some lithium ion complexes journal January 1983
Benchmark calculations with correlated molecular wave functions. I. Multireference configuration interaction calculations for the second row diatomic hydrides journal August 1993
Extremal properties of force constants journal January 1967
Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides journal August 1993
Proton affinities of ammonia, water, and hydrogen fluoride and their anions: a quest for the basis-set limit using the Dunning augmented correlation-consistent basis sets journal January 1993
Many‐body symmetry‐adapted perturbation theory of intermolecular interactions. H 2 O and HF dimers journal November 1991

Cited By (12)

Theoretical study of the desorption of neutral and ionic alkali metal atoms from the excited Li + (H 2 O) n = 1‐4 and Na + (H 2 O) n = 1‐4 cluster models: Electronic excitation charge transfer journal November 2019
Electronic structure, statistical mechanical simulations, and EXAFS spectroscopy of aqueous potassium journal December 2005
Preparation, structure and analysis of the bonding in the molecular entity (OSO)2Li{[AlF(ORF)3]Li[Al(ORF)4]} (RF = C(CF3)3) journal January 2010
The effect of hydration on the electronic structure and stability of the superalkali cation Li 3 + journal January 2018
The hydration structure of the lithium ion journal July 2002
Electronic decay following ionization of aqueous Li+ microsolvation clusters journal March 2005
Ab initio investigation of the N 2 –HF complex: Accurate structure and energetics journal April 1996
Ab initio characterization of the structure and energetics of the ArHF complex journal August 1997
Energy decomposition analysis of intermolecular interactions using a block-localized wave function approach journal April 2000
Structure of the nearest surrounding of the Li+ ion in aqueous solutions of its salts journal February 2006
Hydrated Sodium Ion Clusters [Na+(H2O)n (n = 1–6)]: An ab initio Study on Structures and Non-covalent Interaction journal September 2019
Structure of the Nearest Surrounding of the Li+ Ion in Aqueous Solutions of Its Salts journal September 2006

Figures / Tables (22)

Table 1(p. 3)table Table 1
Figure 1(p. 4)figure Figure 1
Figure 2(p. 5)figure Figure 2
Table II(p. 5)table Table II
Figure 3(p. 6)figure Figure 3
Table III(p. 6)table Table III
Figure 4(p. 7)figure Figure 4
n-l or n-2 points." data-ostiid="1491727">
Figure 5(p. 7)figure Figure 5
Figure 6(p. 7)figure Figure 6
Figure 7(p. 8)figure Figure 7
Table IV(p. 9)table Table IV
Table V(p. 10)table Table V
Figure 8(p. 11)figure Figure 8
Table VI(p. 11)table Table VI
Figure 9(p. 12)figure Figure 9
Table VII(p. 12)table Table VII
Figure 10(p. 13)figure Figure 10
Figure 11(p. 13)figure Figure 11
Table IX(p. 14)table Table IX
Table VIII(p. 14)table Table VIII
Table X(p. 15)table Table X
Figure 13(p. 16)figure Figure 13

Similar Records

An extended basis set [ital ab] [ital initio] study of Li[sup +](H[sub 2]O)[sub [ital n]], [ital n]=1--6
Journal Article · Fri Apr 01 00:00:00 EST 1994 · Journal of Chemical Physics · OSTI ID:1491727
+1 more
Cation-water interactions. The M[sup +](H[sub 2]O)[sub n] clusters for alkali metals, M = Li, Na, K, Rb, and Cs
Journal Article · Thu Mar 09 00:00:00 EST 1995 · Journal of Physical Chemistry; (United States) · OSTI ID:1491727
Geometric and electronic structure of small copper clusters Cu/sub n/ and Cu/sup +//sub n/ (n = 1--3) by an effective core potential method
Journal Article · Wed May 15 00:00:00 EDT 1985 · J. Chem. Phys.; (United States) · OSTI ID:1491727

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY