The Criegee intermediates are carbonyl oxides that play critical roles in ozonolysis of alkenes in the atmosphere. So far, the mid-infrared spectrum of only the simplest Criegee intermediate CH2OO has been reported. Methyl substitution of CH2OO produces two conformers of CH3CHOO and consequently complicates the infrared spectrum. Here we report the… (More)
Prediction of a false ground state with popular variants of multireference perturbation theory (CASPT2 and MRMP) is reported for a remarkably simple chemical system: the Sc(2) molecule.
A detailed analysis of a severe intruder state problem in the multistate multireference perturbation theory (MS-MRPT) calculations on the ground state of manganese dimer is presented. An enormous number of detected intruder states (> 5000) do not permit finding even an approximate shape of the X(1)Sigma(g) (+) potential energy curve. The intruder states are… (More)
The second-order multireference perturbation theory using an optimized partitioning, denoted as MROPT(2), is applied to calculations of various molecular properties-excitation energies, spectroscopic parameters, and potential energy curves-for five molecules: ethylene, butadiene, benzene, N(2), and O(2). The calculated results are compared with those… (More)
A new perturbation approach is proposed that enhances the low-order, perturbative convergence by modifying the zeroth-order Hamiltonian in a manner that enlarges any small-energy denominators that may otherwise appear in the perturbative expansion. This intruder state avoidance (ISA) method can be used in conjunction with any perturbative approach, but is… (More)