Quantum-chemical computational methods are benchmarked for their ability to describe conical intersections in a series of organic molecules and models of biological chromophores. Reference results for the geometries, relative energies, and branching planes of conical intersections are obtained using ab initio multireference configuration interaction with single and double excitations (MRCISD). They are compared with the results from more approximate methods, namely, the state-interaction state-averaged restricted ensemble-referenced Kohn-Sham method, spin-flip time-dependent density functional theory, and a semiempirical MRCISD approach using an orthogonalization-corrected model. It is demonstrated that these approximate methods reproduce the ab initio reference data very well, with root-mean-square deviations in the optimized geometries of the order of 0.1 Å or less and with reasonable agreement in the computed relative energies. A detailed analysis of the branching plane vectors shows that all currently applied methods yield similar nuclear displacements for escaping the strong non-adiabatic coupling region near the conical intersections. Our comparisons support the use of the tested quantum-chemical methods for modeling the photochemistry of large organic and biological systems. © 2014 AIP Publishing LLC. [http://dx

Two new light-driven molecular rotary motors based on the N-alkylated indanylidene benzopyrrole frameworks are proposed and studied using quantum chemical calculations and nonadiabatic molecular dynamics simulations. These new motors perform pure axial rotation, and the photochemical steps of the rotary cycle are dominated by the fast bond-length-alternation motion that enables ultrafast access to the S1/S0 intersection. The new motors are predicted to display a quantum efficiency higher than that of the currently available synthetic all-hydrocarbon motors. Remarkably, the quantum efficiency is not governed by the topography (peaked versus sloped) of the minimum-energy conical intersection, whereas the S1 decay time depends on the topography as well as on the energy of the intersection relative to the S1 minimum. It is the axial chirality (helicity), rather than the point chirality, that controls the sense of rotation of the motor.

AlGaN samples grown by plasma-assisted molecular-beam epitaxy on sapphire (0001) substrates, with 20%–50% Al content and without the use of indium, show intense room-temperature photoluminescence that is significantly redshifted, 200–400meV, from band edge. This intense emission is characterized by a long room-temperature lifetime (∼375ps) comparable to that seen in low defect density (∼108cm−2) GaN. Room-temperature monochromatic cathodoluminescence images at the redshifted peak reveal spatially nonuniform emission similar to that observed in In(Al)GaN alloys and attributed to compositional inhomogeneity. These observations suggest that spatial localization enhances the luminescence efficiency despite the high defect density (>1010cm−2) of the films by inhibiting movement of carriers to nonradiative sites.

Conical intersections are perhaps the most significant mechanistic features of chemical reactions occurring through excited states. By providing funnels for efficient non-adiabatic population transfer, conical intersections govern the branching ratio of products of such reactions, similar to what the transition states do for ground-state reactivity. In this regard, intersections between the ground and the lowest excited states play a special role, and the correct description of the potential energy surfaces in their vicinity is crucial for understanding the mechanism and dynamics of excited-state reactions. The methods of density functional theory, such as time-dependent density functional theory, are widely used to describe the excited states of large molecules. However, are these methods suitable for describing the conical intersections or do they lead to artifacts and, consequently, to erroneous description of reaction dynamics? Here we address the first part of this question and analyze the ability of several density functional approaches, including the linear-response time-dependent approach as well as the spin-flip and ensemble formalisms, to provide the correct description of conical intersections and the potential energy surfaces in their vicinity. It is demonstrated that the commonly used linear-response time-dependent theory does not yield a proper description of these features and that one should instead use alternative computational approaches.

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