IVO‐SSMRPT is an affordable and accurate type of state‐specific multireference perturbation (SSMRPT) theory that adds dynamic correlation energy to improved virtual orbital (IVO) complete active space configuration interaction (CASCI) wave functions using a single‐root parametrization of multi‐root Hilbert‐space ansatz. We applied it to many chemically important di‐ and tri‐radicals to analyze the geometries and electronic properties of spectroscopic interest for both closed‐ and open‐shell singlet‐ and nonsinglet ground as well as excited states. We observed that IVO‐SSMRPT identifies optimized geometries, splitting between multiplets and frequencies for several radicals that are similar to those displayed by current generation state‐of‐the‐art methods but with admiringly decreased computational effort. This study illustrates the importance of having an accurate treatment of both nondynamical and dynamical correlation effects when examining multiradical species. Chemically and spectroscopically relevant answers can be obtained using our computationally tractable method. Our method will be a serviceable avenue for portraying open‐shell interactions in other radicals.

Adaptation of improved virtual orbital complete active space configuration interaction functions in state-specific multireference perturbation theory motivated by the Brillouin-Wigner perturbation scheme using Møller-Plesset multipartitioning is examined. The method, denoted as IVO-BWMRPT, focuses on only the root of principal interest at a time using single-root parameterization of Jeziorski-Monkhorst ansatz within the frame of an effective Hamiltonian. This approach yields size-extensive energy and avoids intruder-state problems in a natural manner. It allows relaxation of the reference space wave function in the presence of the perturbation which produces an important differential effect on the energy and cannot be neglected for quasidegenerate electronic states. The method has been tested against nontrivial situations such as the Be + H2 insertion profile along with the energy surfaces of FH and X2 (X = F, Cl, and Br), in which conventional single-reference methods generally fail, exhibiting very encouraging findings. We also consider the energy surfaces of ethylene (by breaking the π bond as well as the CC bond) and for the twisting of tetramethyleneethane. IVO-BWMRPT represents a rather balanced protocol for the description of molecules at a wide range of geometries, including stretched or dissociating bonds. Close agreement of our estimates with the reference values provides a useful measure for the success of the IVO-BWMRPT method to treat strongly correlated systems. Our results for TME show that the singlet state always lies below the triplet state for different conformations. The IVO-BWMRPT furnishes a compact and correct representation of the MR-wave function, and hence, a large variety of quasidegenerate situations can be accommodated within the method.

No abstract

To compute the electronic excitation energies, a state-specific multireference Møller–Plesset perturbation theory (SSMRPT) with a complete active space configuration interaction reference function constructed using the orbitals obtained by the density functional theory (DFT) is presented as an accurate, as well as computationally affordable, and efficient protocol at the level of second order. The global hybrid B3LYP (Becke, 3-parameter, Lee–Yang–Parr) functional has been used to generate orbitals. The present method, called DFT-SSMRPT, uses perturbers that are individual Slater determinants and accounts for the coupling between the nondynamical and dynamical correlation effects. We have applied the new method to compute excitation energies in conjugated systems of π-electrons such as trans-1,3-butadiene, trans,trans-1,3,5-hexatriene, and all-trans-1,3,5,7-octatetraene. The ordering of the excited states is correctly reproduced by the DFT-SSMRPT calculations. The relative ordering of low-lying excited 1Bu and 1Ag states alters when the length of the polyene changes. The results match reasonably well with the literature including experimental and best theoretical findings. The accuracy of the method is sufficient to discern the energy gap between the close low-lying singlet and triplet states. The DFT-SSMRPT appears as an affordable computational ab initio avenue for a qualitatively correct description of excitation energies.

No abstract