Excitonic Configuration Interaction: Going Beyond the Frenkel Exciton Model.

We present the excitonic configuration interaction (ECI) method─a fragment-based analogue of the CI method for electronic structure calculations of multichromophoric systems. It can also be viewed as a generalization of the exciton approach, with the following properties: (i) It constructs the effective Hamiltonian exclusively from monomer calculations. (ii) It employs the strong orthogonality assumption and is exact within McWeeny's group function theory, thus requiring only one-electron density matrices of the monomer states. (iii) It is agnostic of the monomer electronic structure method, allowing us to use/combine different methods. (iv) It includes an embedding point charge scheme (called excitonic Hartree-Fock, EHF) to improve the accuracy of the monomer states, but such that the effective full-system Hamiltonian is not explicitly dependent on the embedding. (v) It is systematically improvable, by expanding the set of monomer states and by including configurations where two or more monomers are excited (defining the ECIS, ECISD, etc., methods). The performance of ECI is assessed by computing the absorption spectrum of two exemplary multichromophoric systems, using CIS as the monomer electronic structure method. The accuracy of ECI significantly depends on the chosen embedding charges and the ECI expansion. The most accurate assessed combinations─ECIS or ECISD with EHF embedding─yield spectra that agree qualitatively and quantitatively with full-system direct calculations, with deviations of the excitation energies below 0.1 eV. We also show that ECISD based on CIS monomer calculations can predict states where two monomers are excited simultaneously (e.g., triplet-triplet double-local excitations) that are inaccessible in a full-system CIS calculation.

Photochemical Ring-Opening Reaction of 1,3-Cyclohexadiene: Identifying the True Reactive State.

The photochemically induced ring-opening isomerization reaction of 1,3-cyclohexadiene to 1,3,5-hexatriene is a textbook example of a pericyclic reaction and has been amply investigated with advanced spectroscopic techniques. The main open question has been the identification of the single reactive state which drives the process. The generally accepted description of the isomerization pathway starts with a valence excitation to the lowest lying bright state, followed by a passage through a conical intersection to the lowest lying doubly excited state, and finally a branching between either the return to the ground state of the cyclic molecule or the actual ring-opening reaction leading to the open-chain isomer. Here, in a joint experimental and computational effort, we demonstrate that the evolution of the excitation-deexcitation process is much more complex than that usually described. In particular, we show that an initially high-lying electronic state smoothly decreasing in energy along the reaction path plays a key role in the ring-opening reaction.

Anticooperativity of Multiple Halogen Bonds and Its Effect on Stoichiometry of Cocrystals of Perfluorinated Iodobenzenes.

To investigate influences on the topicity of perfluorinated halobenzenes as halogen bond (XB) donors in the solid state, we have conducted a database survey and prepared 18 novel cocrystals of potentially ditopic (13ditfb, 14ditfb) and tritopic (135titfb) XB donors with 15 monotopic pyridines. 135titfb shows high tendency to be mono- or ditopic, but with strong bases it can act as a tritopic XB donor. DFT calculations have shown that binding of a single acceptor molecule on one of the iodine atoms of the XB donor reduces the ESPmax on the remaining iodine atoms and dramatically decreases their potential for forming further halogen bonds, which explains both the high occurrence of crystal structures where the donors do not achieve their maximal topicity and the observed differences in halogen bond lengths. Despite the fact that this effect increases with the basicity of the acceptor, when the increase of halogen bond energy due to the basicity of the acceptor compensates its decrease due to the reduction of the acidity of the donor, it enables strong bases to form cocrystals in which a potentially polytopic XB donor achieves its maximal topicity.

Combined Surface-Hopping, Dyson Orbital, and B-Spline Approach for the Computation of Time-Resolved Photoelectron Spectroscopy Signals: The Internal Conversion in Pyrazine.

A computational protocol for simulating time-resolved photoelectron signals of medium-sized molecules is presented. The procedure is based on a trajectory surface-hopping description of the excited-state dynamics and a combined Dyson orbital and multicenter B-spline approach for the computation of cross sections and asymmetry parameters. The accuracy of the procedure has been illustrated for the case of ultrafast internal conversion of gas-phase pyrazine excited to the 1B2u(ππ*) state. The simulated spectra and the asymmetry map are compared to the experimental data, and a very good agreement was obtained without applying any energy-dependent rescaling or broadening. An interesting side result of this work is the finding that the signature of the 1Au(nπ*) state is indistinguishable from that of the 1B3u(nπ*) state in the time-resolved photoelectron spectrum. By locating four symmetrically equivalent minima on the lowest-excited (S1) adiabatic potential energy surface of pyrazine, we revealed the strong vibronic coupling of the 1Au(nπ*) and 1B3u(nπ*) states near the S1 ← S0 band origin.

Photoelimination of Nitrogen from Diazoalkanes: Involvement of Higher Excited Singlet States in the Carbene Formation.

Although diazoalkanes are important carbene precursors in organic synthesis, a comprehensive mechanism of photochemical formation of carbenes from diazoalkanes has not been proposed. Synergies of experiments and computations demonstrate the involvement of higher excited singlet states in the photochemistry of diazoalkanes. In all investigated diazoalkanes, excitation to S1 results in nonreactive internal conversion to S0. On the contrary, excitation to higher-lying singlet states (Sn, n > 1) drives the reaction toward a different segment of the S1/S0 conical intersection seam and results in nitrogen elimination and formation of carbenes.

Highly Efficient Algorithms for CIS Type Excited State Wave Function Overlaps.

Two algorithms for calculating overlaps between CIS (or TDDFT) type excited state wave functions are presented, one based on an expansion of overlap determinants into level 2 minors (OL2M) and the other based on an expansion of the wave functions into natural transition orbitals (ONTO). Both algorithms are significantly faster than previously available algorithms, with the ONTO algorithm reducing the cost of a single overlap element calculation by a factor of the square of the number of occupied orbitals in the system. The algorithm exhibits orders of magnitude faster calculations for large systems and significantly increases the size of systems for which TDDFT based nonadiabatic dynamics simulations can be performed. The OL2M algorithm is substantially slower for a single overlap matrix element but becomes preferred when overlaps between large numbers of states are required. Additionally, we test the accuracy of approximate overlaps calculated using truncated wave functions and show that truncation can lead to large errors in the overlaps. Lastly, we provide examples of applications for wave function overlaps outside the context of nonadiabatic dynamics.