By combining the generalized valence bond ansatz of correlated participating orbitals (CPO) with the complete-active-space prescription for selecting configurations and with the use of multireference second order perturbation theory (MRMP2) for including dynamical correlation, we define three levels of multireference (MR) theoretical model chemistries for electronic structure calculations of chemical reaction energies and barrier heights. The three levels differ in their choice of which orbitals are considered to be participating; the choices are called nominal (nom-CPO), moderate (mod-CPO), and extended (ext-CPO). Combining any of these three choices with a method for treatment of dynamical correlation energy and a one-electron basis set yields a theoretical model chemistry. Unlike the full-valence choice of active orbitals, the CPO choices lead to active spaces that contain the orbitals needed to include important static correlation effects on chemical reactions but do not increase with the size of the nonparticipating portion of the system, and hence they remain viable computational options even for many large and complex reacting systems. The accuracies of the new levels, combined with the MG3S basis set (a partially augmented, multiply polarized valence triple-ζ basis with appropriately tight d functions for 3p-block elements) and with the fully augmented correlation-consistent aug-cc-pVTZ basis set, are assessed against a previously presented database of barrier heights for diverse reaction types. We find that nom-CPO level captures the bulk of the static correlation energy, and MRMP2/nom-CPO calculations have an average error of only 1.4 kcal/mol in barrier heights, which may be compared to 5.0 kcal/mol for single-reference MP2 theory, 2.5 kcal/mol for CCSD, and 4.1 and 1.0 kcal/mol for the B3LYP and M06-2X density functionals, respectively. The accuracy of MRMP2/CPO for transition structure bond lengths and donor-acceptor distances is excellent, with a mean unsigned error of only 0.007 Å as compared to 0.018 Å for CCSD, 0.019 Å for M06-2X, and 0.039 Å for MP2 and B3LYP. We also introduce a new multireference diagnostic, called the M diagnostic, that allows one to measure the importance of static correlation in a given reagent or transition state.

The 1,3-dipolar cycloadditions of ozone to ethyne and ethene provide extreme examples of multireference singlet-state chemistry, and they are examined here to test the applicability of several approaches to thermochemical kinetics of systems with large static correlation. Four different multireference diagnostics are applied to measure the multireference characters of the reactants, products, and transition states; all diagnostics indicate significant multireference character in the reactant portion of the potential energy surfaces. We make a more complete estimation of the effect of quadruple excitations than was previously available, and we use this with CCSDT/CBS estimation of Wheeler et al. (Wheeler, S. E.; Ess, D. H.; Houk, K. N. J. Phys. Chem. A 2008, 112, 1798 to make new best estimates of the van der Waals association energy, the barrier height, and the reaction energy to form the cycloadduct for both reactions. Comparing with these best estimates, we present comprehensive mean unsigned errors for a variety of coupled cluster, multilevel, and density functional methods. Several computational aspects of multireference reactions are considered: (i) the applicability of multilevel theory, (ii) the convergence of coupled cluster theory for reaction barrier heights, (iii) the applicability of completely renormalized coupled cluster methods to multireference systems, (iv) the treatment by density functional theory, (v) the multireference perturbation theory for multireference reactions, and (vi) the relative accuracy of scaling-type multilevel methods as compared with additive ones. It is found that scaling-type multilevel methods do not perform better than the additive-type multilevel methods. Among the 48 tested density functionals, only M05 reproduces the best estimates within their uncertainty. Multireference perturbation theory based on the complete-active-space reference wave functions constructed using a small number of reaction-specific active orbitals gives accurate forward barrier heights; however, it significantly underestimates reaction energies.

We employed four newly developed density functional theory (DFT) methods for the calculation of five pi hydrogen bonding systems, namely, H2O-C6H6, NH3-C6H6, HCl-C6H6, H2O-indole, and H2O-methylindole. We report new coupled cluster calculations for HCl-C6H6 that support the experimental results of Gotch and Zwier. Using the best available theoretical and experimental results for all five systems, our calculations show that the recently proposed MPW1B95, MPWB1K, PW6B95, and PWB6K methods give accurate energetic and geometrical predictions for pi hydrogen bonding interactions, for which B3LYP fails and PW91 is less accurate. We recommend the most recent DFT method, PWB6K, for investigating larger pi hydrogen bonded systems, such as those that occur in molecular recognition, protein folding, and crystal packing.

The relation between the hydrogen atom transfer (HAT) and proton-coupled electron transfer (PCET) mechanisms is discussed and is illustrated by multiconfigurational electronic structure calculations on the ArOH + R(*) --> ArO(*) + RH reactions. The key topographic features of the Born-Oppenheimer potential energy surfaces that determine the predominant reaction mechanism are the conical intersection seam of the two lowest states and reaction saddle points located on the shoulders of this seam. The saddle point corresponds to a crossing of two interacting valence bond states corresponding to the reactant and product bonding patterns, and the conical intersection corresponds to the noninteracting intersection of the same two diabatic states. The locations of mechanistically relevant conical intersection structures and relevant saddle point structures are presented for the reactions between phenol and the N- and O-centered radicals, (*)NH2 and (*)OOCH3. Points on the conical intersection of the ground doublet D0 and first excited doublet D1 states are found to be in close geometric and energetic proximity to the reaction saddle points. In such systems, either the HAT mechanism or both the HAT mechanism and the proton-coupled electron transfer (PCET) mechanism can take place, depending on the relative energetic accessibility of the reaction saddle points and the D0/D1 conical intersection seams. The discussion shows how the two mechanisms are related and how they blend into each other along intermediate reaction paths. The recognition that the saddle point governing the HAT mechanism is on the shoulder of the conical intersection governing the PCET mechanism is used to provide a unified view of the competition between the two mechanisms (and the blending of the two mechanisms) in terms of the prominent and connected features of the potential energy surface, namely the saddle point and the conical intersection. The character of the dual mechanism may be understood in terms of the dominant valence bond configurations of the intersecting states, which are zero-order approximations to the diabatic states.