Photoinduced proton-coupled electron transfer of hydrogen-bonded p-nitrophenylphenol-methylamine complex in solution.

Proton-coupled electron transfer can occur through concerted (electron-proton transfer, EPT) or sequential mechanisms, but this distinction becomes less well-defined for photoinduced reactions. These issues have been examined with transient absorption experiments on a hydrogen-bonded complex consisting of p-nitrophenylphenol and t-butylamine. These experiments revealed two spectroscopically distinct states: the higher-energy excited state was interpreted to be a conventional intramolecular charge transfer (ICT) state within the p-nitrophenylphenol, whereas the lower-energy state was interpreted to be an ICT-EPT state, where photoexcitation resulted in both ICT and the shifting of electronic density corresponding to effective proton transfer from the phenol to the amine. In the present work, the singlet excited states of the hydrogen-bonded p-nitrophenylphenol-methylamine complex in 1,2-dichloroethane are studied with time-dependent density functional theory and higher-level ab initio methods. The calculations suggest that the ππ* state, which is the S(1) state at the Franck-Condon geometry, corresponds to the state denoted ICT-EPT in the experimental analysis, whereas the nπ* state, which is the S(2) state at this geometry, likely corresponds to the state denoted ICT in the experimental analysis. According to the calculations, the ππ* state has charge-transfer character, as well as a change in electronic density on the amine, with the minimum-energy structure corresponding to the proton bonded to the nitrogen acceptor, consistent with proton transfer. The nπ* state has little charge-transfer character, as well as negligible change in electronic density on the amine, with the minimum-energy structure corresponding to the proton bonded to the oxygen donor. The calculations also provide evidence of an avoided crossing between these two states located energetically close to the Franck-Condon point. These calculations provide the foundation for future nonadiabatic molecular dynamics studies of the relaxation process.

Alternative wavefunction ansatz for including explicit electron-proton correlation in the nuclear-electronic orbital approach.

The nuclear-electronic orbital (NEO) approach treats specified nuclei quantum mechanically on the same level as the electrons with molecular orbital techniques. The explicitly correlated Hartree-Fock (NEO-XCHF) approach was developed to incorporate electron-nucleus dynamical correlation directly into the variational optimization of the nuclear-electronic wavefunction. In the original version of this approach, the Hartree-Fock wavefunction is multiplied by (1+G), where G is a geminal operator expressed as a sum of Gaussian type geminal functions that depend on the electron-proton distance. Herein, a new wavefunction ansatz is proposed to avoid the computation of five- and six-particle integrals and to simplify the computation of the lower dimensional integrals involving the geminal functions. In the new ansatz, denoted NEO-XCHF2, the Hartree-Fock wavefunction is multiplied by √(1+G) rather than (1+G). Although the NEO-XCHF2 ansatz eliminates the integrals that are quadratic in the geminal functions, it introduces terms in the kinetic energy integrals with no known analytical solution. A truncated expansion scheme is devised to approximate these problematic terms. An alternative hybrid approach, in which the kinetic energy terms are calculated with the original NEO-XCHF ansatz and the potential energy terms are calculated with the NEO-XCHF2 ansatz, is also implemented. Applications to a series of model systems with up to four electrons provide validation for the NEO-XCHF2 approach and the treatments of the kinetic energy terms.

Photodynamics in complex environments: ab initio multiple spawning quantum mechanical/molecular mechanical dynamics.

Our picture of reactions on electronically excited states has evolved considerably in recent years, due to advances in our understanding of points of degeneracy between different electronic states, termed "conical intersections" (CIs). CIs serve as funnels for population transfer between different electronic states, and play a central role in ultrafast photochemistry. Because most practical photochemistry occurs in solution and protein environments, it is important to understand the role complex environments play in directing excited-state dynamics generally, as well as specific environmental effects on CI geometries and energies. In order to model such effects, we employ the full multiple spawning (FMS) method for multistate quantum dynamics, together with hybrid quantum mechanical/molecular mechanical (QM/MM) potential energy surfaces using both semiempirical and ab initio QM methods. In this article, we present an overview of these methods, and a comparison of the excited-state dynamics of several biological chromophores in solvent and protein environments. Aqueous solvation increases the rate of quenching to the ground state for both the photoactive yellow protein (PYP) and green fluorescent protein (GFP) chromophores, apparently by energetic stabilization of their respective CIs. In contrast, solvation in methanol retards the quenching process of the retinal protonated Schiff base (RPSB), the rhodopsin chromophore. Protein environments serve to direct the excited-state dynamics, leading to higher quantum yields and enhanced reaction selectivity.

Pseudospectral time-dependent density functional theory.

Time-dependent density functional theory (TDDFT) is implemented within the Tamm-Dancoff approximation (TDA) using a pseudospectral approach to evaluate two-electron repulsion integrals. The pseudospectral approximation uses a split representation with both spectral basis functions and a physical space grid to achieve a reduction in the scaling behavior of electronic structure methods. We demonstrate here that exceptionally sparse grids may be used in the excitation energy calculation, following earlier work employing the pseudospectral approximation for determining correlation energies in wavefunction-based methods with similar conclusions. The pseudospectral TDA-TDDFT method is shown to be up to ten times faster than a conventional algorithm for hybrid functionals without sacrificing chemical accuracy.

Ab initio excited-state dynamics of the photoactive yellow protein chromophore.

The photoisomerization mechanism of the neutral form of the photoactive yellow protein (PYP) chromophore is investigated using ab initio quantum chemistry and first-principles nonadiabatic molecular dynamics (ab initio multiple spawning or AIMS). We identify the nature of the two lowest-lying excited states, characterize the short-time behavior of molecules excited directly to S2, and explain the origin of the experimentally observed wavelength-dependent photoisomerization quantum yield.