For a variety of density functional theories, we examined the ground-state properties of the water monomer (geometry, vibrational frequencies, dipole moment, polarizability) and dimer (geometry, vibrational frequencies, bond energy, and barrier heights for the transition states for the interchange of hydrogen atoms within the dimer). Thus, we considered LDA (SVWN), seven pure GGA methods (BLYP, BP86, BPW91, PWPW, mPWPW, PBEPBE, and XLYP), and eight hybrid GGA methods (BH&HLYP, B3LYP, B3P86, B3PW91, PW1PW, mPW1PW, PBE1PBE and X3LYP). We find that the best overall performance is given by X3LYP, a hybrid method using a modified GGA constructed from a linear combination of the Becke and Perdew GGAs. Comparing with the exact values, the errors in X3LYP for the water dimer are 0.05 kcal/mol (bond energy), 0.004

After exploring the underlying physics of the cluster-surface analogy, we introduce the concept of "metallic atom". Case studies of the Ni-CO cluster as a model of CO/Ni chemisorption are carried out with UHF,/STO-3G of the so-called atomic ζa and metallic ζm, where ζa is a basis function optimized from the ground state of a Ni atom, while ζm is a modifier of ζa based on the free-electron theory in solid state physics. The calculation results of ζa and ζm are elucidated in the light of more rigorous cluster calculations in the literature.

Three principles, namely, a neutrality princi-ple, a stoichiometry principle, and a coordination principle are proposed as criteria for building up cluster models of metal oxides. Particular attention is focused on how to cut out a stoichiometric cluster which possesses the smallest boundary e

We derive the form for an exact exchange energy density for a density decaying with Gaussian-like behavior at long range. Based on this, we develop the X3LYP (extended hybrid functional combined with Lee-Yang-Parr correlation functional) extended functional for density functional theory to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energies [over the most popular and accurate method, B3LYP (Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional)]. X3LYP also leads to a good description of dipole moments, polarizabilities, and accurate excitation energies from s to d orbitals for transition metal atoms and ions. We suggest that X3LYP will be useful for predicting ligand binding in proteins and DNA.

The recent observation [Wentworth, P., Jones, L. H., Wentworth, A. D., Zhu, X. Y., Larsen, N. A., Wilson, I. A., Xu, X., Goddard, W. A., Janda, K. D., Eschenmoser, A. & Lerner, R. A. (2001) Science 293, 1806–1811] that antibodies form H2O2 from 1O2 plus H2O was explained in terms of the formation of the H2O3 species that in the antibody reacts with a second H2O3 to form H2O2. There have been few reports of the chemistry for forming H2O3, but recently Engdahl and Nelander [Engdahl, A. & Nelander, B. (2002) Science 295, 482-483] reported that photolysis of the ozone-hydrogen peroxide complex in argon matrices leads to significant concentrations of H2O3. We report here the chemical mechanism for this process, determined by using first-principles quantum mechanics. We show that in an argon matrix it is favorable (3.5 kcal mol barrier) for H2O2 and O3 to form a [(HO2)(HO3)] hydrogen-bonded complex [head-to-tail sevenmembered ring (7r)]. In this complex, the barrier for forming H2O3 plus 3O2 is only 4.8 kcal mol, which should be observable by means of thermal processes (not yet reported). Irradiation of the [(HO2)(HO3)-7r] complex should break the HO–OO bond of the HO3 moiety, eliminating 3O2 and leading to [(HO2)(HO)]. This [(HO2)(HO)] confined in the matrix cage is expected to rearrange to also form H2O3 (observed experimentally). We show that these two processes can be distinguished isotopically. These results (including the predicted vibrational frequencies) suggest strategies for synthesizing H2O3 and characterizing its chemistry. We suggest that the [(HO2)(HO3)-7r] complex and H2O3 are involved in biological, atmospheric, and environmental oxidative processes.