New algorithms for optimizing and linking conical intersection points

In this paper we present two new algorithms to study the extended nature of the crossing seam between electronic potential energy surfaces. The first algorithm is designed to optimize conical intersection geometries: both minima and saddle points. In addition, this method will optimize conical intersection geometries using arbitrary geometrical constraints. We demonstrate its potential on different crossing seams of benzene, z-penta-3,5-dleniminium, and 1,3-butadiene. The second algorithm is designed to explicitly compute the intersection-space minimum energy coordinate. Our computations show how an intersection seam and the energy along it can be unambiguously defined. A finite region of the S0/S11,3-butadiene crossing seam has been mapped out, and a new saddle point linked with two lower-lying geometries on the sea

Unlocking the Double Bond in Protonated Schiff Bases by Coherent Superposition of S_{1} and S_{2}

The primary event occurring during the E-to-Z photoisomerization reaction of retinal protonated Schiff base (rPSB) is single-to-double bond inversion. In this work we examine the nuclear dynamics that occurs when the initial excited state is a superposition of the S_{1} and S_{2} electronic excited states that might be created in a laser experiment. The nuclear dynamics is dominated by double bond inversion that is parallel to the derivative coupling vector of S_{1} and S_{2}. Thus, the molecule behaves as if it were at a conical intersection even if the states are nondegenerate

A definition of the magnetic transition temperature using valence bond theory

Macroscopic magnetic properties are analyzed using Valence Bond theory. Commonly the critical temperature TC for magnetic systems is associated with a maximum in the energy-based heat capacity Cp(T). Here a more broadly applicable definition of the magnetic transition temperature TC is described using spin moment expectation value (i.e. applying the spin exchange density operator) instead of energy. Namely, the magnetic capacity Cs(T) reflects variation in the spin multiplicity as a function of temperature, which is shown to be related to ∂[χT(T)]/∂T. Magnetic capacity Cs(T) depends on long-range spin interactions that are not relevant in the energy-based heat capacity Cp(T). Differences between Cs(T) and Cp(T) are shown to be due to spin order/disorder within the crystal, that can be monitored via a Valence Bond analysis of the corresponding magnetic wavefunction. Indeed the concept of the Boltzmann spin-alignment order is used to provide information about the spin correlation between magnetic units. As a final illustration, the critical temperature is derived from the magnetic capacity for several molecular magnets presenting different magnetic topolo- gies that have been experimentally studied. A systematic shift between the transition temperatures associated with Cs(T) and Cp(T) is observed. It is demonstrated that this shift can be attributed to the loss of long-range spin correlation. This suggests that the magnetic capacity Cs(T) can be used as a predictive tool for the magnetic topology, and thus for the synthetic chemists

Electron dynamics following photoionization: decoherence due to the nuclear-wave-packet width

The advent of attosecond techniques opens up the possibility to observe experimentally electron dynamics following ionization of molecules. Theoretical studies of pure electron dynamics at single fixed nuclear geometries in molecules have demonstrated oscillatory charge migration at a well-defined frequency but often neglecting the natural width of the nuclear wave packet. The effect on electron dynamics of the spatial delocalization of the nuclei is an outstanding question. Here, we show how the inherent distribution of nuclear geometries leads to dephasing. Using a simple analytical model, we demonstrate that the conditions for a long-lived electronic coherence are a narrow nuclear wave packet and almost parallel potential-energy surfaces of the states involved. We demonstrate with numerical simulations the decoherence of electron dynamics for two real molecular systems (paraxylene and polycyclic norbornadiene), which exhibit different decoherence time scales. To represent the quantum distribution of geometries of the nuclear wave packet, the Wigner distribution function is used. The electron dynamics decoherence result has significant implications for the interpretation of attosecond spectroscopy experiments since one no longer expects long-lived oscillations

Photochemical reaction paths of cis-dienes studied with RASSCF: the changing balance between ionic and covalent excited states

International audienc

Coherent mixing of singlet and triplet states in acrolein and ketene: a computational strategy for simulating the electron-nuclear dynamics of intersystem crossing.

We present a theoretical study of intersystem crossing (ISC) in acrolein and ketene with the Ehrenfest method that can describe a superposition of singlet and triplet states. Our simulations illustrate a new mechanistic effect of ISC, namely, that a superposition of singlets and triplets yields nonadiabatic dynamics characteristic of that superposition rather than the constituent state potential energy surfaces. This effect is particularly significant in ketene, where mixing of singlet and triplet states along the approach to a singlet/singlet conical intersection occurs, with the spin-orbit coupling (SOC) remaining small throughout. In both cases, the effects require many recrossings of the singlet/triplet state crossing seam, consistent with the textbook treatment of ISC

Arginine52 controls the photoisomerization process in photoactive yellow protein

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Charge migration engineered by localisation: electron-nuclear dynamics in polyenes and glycine

We demonstrate that charge migration can be ‘engineered’ in arbitrary molecular systems if a single localised orbital – that diabatically follows nuclear displacements – is ionised. Specifically, we describe the use of natural bonding orbitals in Complete Active Space Configuration Interaction (CASCI) calculations to form cationic states with localised charge, providing consistently well-defined initial conditions across a zero point energy vibrational ensemble of molecular geometries. In Ehrenfest dynamics simulations following localised ionisation of -electrons in model polyenes (hexatriene and decapentaene) and -electrons in glycine, oscillatory charge migration can be observed for several femtoseconds before dephasing. Including nuclear motion leads to slower dephasing compared to fixed-geometry electron-only dynamics results. For future work, we discuss the possibility of designing laser pulses that would lead to charge migration that is experimentally observable, based on the proposed diabatic orbital approach