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We present our computational implementation of the spin-flip (SF) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and (full) triples (SDT) within Q-CHEM. The inclusion of triples not only enhances the quantitative accuracy of the SF-EOM-CCSD method but also provides correct qualitative trends in the energy gaps between strongly degenerate states. To assess the accuracy, we compare our SF-EOM-CCSDT results with full configuration interaction (FCI) and complete-active-space self-consistent field second-order (CASSCF-SO) CI benchmarks to study the adiabatic energy gaps in CH 2 and NH 2 + diradicals, vertical excitation energies in CH radicals and the bond dissociation of the HF molecule. We have implemented SF-EOM-CCSDT using both the conventional double precision (DP) and the single precision (SP) algorithms. The use of SP does not introduce any significant errors in energies and energy gaps, and, due to low cost (relative to DP), turns out to be a promising approach to widen the applicability of EOM-CCSDT to bigger molecules.

Computational studies were performed on non-classical thieno[3,4-c][1,2,5] thiadiazole and its pi donor derivatives (TT dyes) so as to delineate the factors responsible for their near-infrared (NIR) absorption. For all dyes except the unsubstituted bare dye, adiabatic singlet-triplet energy gaps (estimated through the ΔSCF procedure using the B3LYP and M062X DFT methods and SFTDDFT with the 5050 functional) were less than 1eV. Percentage calculations of the biradicaloid character suggested a moderate biradicaloid nature in all derivatives. There was a resemblance between the frontier molecular orbital (MO) picture of the TT bicyclic ring and the degenerate non-bonding molecular orbitals of Trimethyleneethane (TME, a known biradical). Inter-fragment charge transfer analysis revealed not only a considerable donation of charge to the central ring (Acceptor, TT part) but also substantial charge redistribution within the ring itself. From these results, it was inferred that NIR absorption, in these dyes, was due to: (1) a reduced HOMO-LUMO gap (HLG) as a TME biradical substructure forms its chromophoric part; and (2) charge transfer from the donor substituents. The non-bonding nature of the S atom, in the bare dye, with its neighbouring N/C atom (of the highest occupied π-MOs), led to an examination of its electronic structure using the ab initio valence bond method. The relatively large weight and energetic stability of the biradicaloid VB structures compared to those of the ylidic structures clearly disclosed the importance of biradicaloid structures in the overall resonance of the bare dye. Their utility as singlet fission materials was screened using singlet and triplet energy-based molecular structure activity criteria. The results were encouraging, demanding experiments to reaffirm the materials' usefulness.

Fock space multireference coupled-cluster (FSMRCC) method emerged as an efficient tool to describe the electronic structure of nearly degenerate cases. Development of linear response has been one of the challenging problems in FSMRCC due to the multiple-root nature of the effective Hamiltonian. A response from any of the roots would span the space for getting the properties. Hence, all roots perturbed by the external field would proliferate the excited states. We recently developed the FSMRCC method for the efficient evaluation of analytic response properties using a constrained variation approach. In this paper, we present analytic dipole moments and polarizabilities of H(2)O, O(3), and CH(+) molecules in low-lying excited states along with brief discussion of singlet triplet decoupling of (1,1) sector of FSMRCC resulting from spin adaptation.