Multistate Energy Decomposition Analysis of Molecular Excited States.

A multistate energy decomposition analysis (MS-EDA) method is described to dissect the energy components in molecular complexes in excited states. In MS-EDA, the total binding energy of an excimer or an exciplex is partitioned into a ground-state term, called local interaction energy, and excited-state contributions that include exciton excitation energy, superexchange stabilization, and orbital and configuration-state delocalization. An important feature of MS-EDA is that key intermediate states associated with different energy terms can be variationally optimized, providing quantitative insights into widely used physical concepts such as exciton delocalization and superexchange charge-transfer effects in excited states. By introducing structure-weighted adiabatic excitation energy as the minimum photoexcitation energy needed to produce an excited-state complex, the binding energy of an exciplex and excimer can be defined. On the basis of the nature of intermolecular forces through MS-EDA analysis, it was found that molecular complexes in the excited states can be classified into three main categories, including (1) encounter excited-state complex, (2) charge-transfer exciplex, and (3) intimate excimer or exciplex. The illustrative examples in this Perspective highlight the interplay of local excitation polarization, exciton resonance, and superexchange effects in molecular excited states. It is hoped that MS-EDA can be a useful tool for understanding photochemical and photobiological processes.

Block-Localized Excitation for Excimer Complex and Diabatic Coupling.

We describe a block-localized excitation (BLE) method to carry out constrained optimization of block-localized orbitals for constructing valence bond-like, diabatic excited configurations using multistate density functional theory (MSDFT). The method is an extension of the previous block-localized wave function method through a fragment-based ΔSCF approach to optimize excited determinants within a molecular complex. In BLE, both the number of electrons and the electronic spin of different fragments in a whole system can be constrained, whereas electrostatic, exchange, and polarization interactions among different blocks can be fully taken into account of. To avoid optimization collapse to unwanted states, a ΔSCF projection scheme and a maximum overlap of wave function approach have been presented. The method is illustrated by the excimer complex of two naphthalene molecules. With a minimum of eight spin-adapted configurational state functions, it was found that the inversion of La- and Lb- states near the optimal structure of the excimer complex is correctly produced, which is in quantitative agreement with DMRG-CASPT2 calculations and experiments. Trends in the computed transfer integrals associated with excited-state energy transfer both in the singlet and triplet states are discussed. The results suggest that MSDFT may be used as an efficient approach to treat intermolecular interactions in excited states with a minimal active space (MAS) for interpretation of the results and for dynamic simulations, although the selection of a small active space is often system dependent.

Minimal-active-space multistate density functional theory for excitation energy involving local and charge transfer states.

Multistate density functional theory (MSDFT) employing a minimum active space (MAS) is presented to determine charge transfer (CT) and local excited states of bimolecular complexes. MSDFT is a hybrid wave function theory (WFT) and density functional theory, in which dynamic correlation is first incorporated in individual determinant configurations using a Kohn-Sham exchange-correlation functional. Then, nonorthogonal configuration-state interaction is performed to treat static correlation. Because molecular orbitals are optimized separately for each determinant by including Kohn-Sham dynamic correlation, a minimal number of configurations in the active space, essential to representing low-lying excited and CT states of interest, is sufficient to yield the adiabatic states. We found that the present MAS-MSDFT method provides a good description of covalent and CT excited states in comparison with experiments and high-level computational results. Because of the simplicity and interpretive capability through diabatic configuration weights, the method may be useful in dynamic simulations of CT and nonadiabatic processes.