A procedure based on the reproducing kernel Hilbert space ͑RKHS͒ interpolation method has been implemented to produce a globally smooth potential energy surface ͑PES͒ for the 1 AЈ state of the S( 1 D)ϩH 2 reaction from a set of accurate ab initio data, calculated at the multireference configuration interaction level with augmented polarized quadruple-zeta basis sets and arranged on a three-dimensional regular full grid in the Jacobi coordinates. The procedure includes removing a small number of questionable ab initio data points, implementing a recently developed technique for efficiently handling a partially filled grid, and adopting a sequence of regularizations for attaining additional smoothness. The resulting RKHS PES is analytic, first-order differentiable, and fast to evaluate. Quasiclassical trajectory calculations have been performed and compared with the results based on a recent hybrid PES obtained from a combination of the RKHS interpolation in the entrance channel and Murrell-Carter ͑MC͒-type fitting in the exit channel from the same set of ab initio data. Comparisons with recent experimental measurements show improvement of the present RKHS PES over the existing hybrid RKHS-MC PES. The results demonstrate that the entrance channel Jacobi coordinates can still be a good candidate in sampling the full configuration space for reactive systems involving three atoms.

A new ab initio potential energy surface is generated for the chemical reaction, S(1D)+H2. The quantum chemistry calculations were carried out at the multi-reference configuration interaction (MRCI) level with multi-configuration self-consistent field (MCSCF) reference wave functions. The 1A′, 2A′, 3A′, 1A″, and 2A″ singlet surfaces were computed on a uniform spatial grid of over 2000 points to simulate the full reaction pathway. The results indicate a barrierless insertion pathway along the T-shaped geometry and an 8 kcal/mol barrier to abstraction along the collinear geometry. The lowest surface was fit to a smooth analytical function form based on the reproducing kernel Hilbert space approach and a Carter–Murrell-type expansion. The dynamics of the S(1D)+H2/D2 reactions were simulated using the quasi-classical trajectory method. The results are generally consistent with an insertion mechanism mediated through capture dynamics in the entrance channel followed by the statistical decay of a long-lived complex. Comparison to recent molecular beam experiments shows agreement in the broad pattern of results but also exhibits significant differences in the more finely resolved quantities.

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Quantum chemical calculations of geometric and electronic structure and vertical transition energies for several low-lying excited states of the neutral and negatively charged nitrogen-vacancy point defect in diamond (NV(0) and NV(-)) have been performed employing various theoretical methods and basis sets and using finite model NC(n)H(m) clusters. Unpaired electrons in the ground doublet state of NV(0) and triplet state of NV(-) are found to be localized mainly on three carbon atoms around the vacancy and the electronic density on the nitrogen and rest of C atoms is only weakly disturbed. The lowest excited states involve different electronic distributions on molecular orbitals localized close to the vacancy and their wave functions exhibit a strong multireference character with significant contributions from diffuse functions. CASSCF calculations underestimate excitation energies for the anionic defect and overestimate those for the neutral system. The inclusion of dynamic electronic correlation at the CASPT2 level leads to a reasonable agreement (within 0.25 eV) of the calculated transition energy to the lowest excited state with experiment for both systems. Several excited states for NV(-) are found in the energy range of 2-3 eV, but only for the 1(3)E and 5(3)E states the excitation probabilities from the ground state are significant, with the first absorption band calculated at approximately 1.9 eV and the second lying 0.8-1 eV higher in energy than the first one. For NV(0), we predict the following order of electronic states: 1(2)E (0.0), 1(2)A(2) (approximately 2.4 eV), 2(2)E (2.7-2.8 eV), 1(2)A(1), 3(2)E (approximately 3.2 eV and higher).