An overview of nonadiabatic dynamics simulations methods, with focus on the direct approach versus the fitting of potential energy surfaces

We review state-of-the-art nonadiabatic molecular dynamics methods, with focus on the comparison of two general strategies: the "direct" one, in which the potential energy surfaces (PES) and the couplings between electronic states are computed during the integration of the dynamics equations; and the "PES-fitting" one, whereby the PES and couplings are preliminarily computed and represented as functions of the nuclear coordinates. Both quantum wavepacket dynamics (QWD) and classical trajectory approaches are considered, but we concentrate on methods for which the direct strategy is viable: among the QWD ones, we focus on those based on traveling basis functions. We present several topics in which recent progress has been made: quantum decoherence corrections in trajectory methods, the use of quasi-diabatic representations, the sampling of initial conditions and the inclusion of field-molecule interactions and of spin-orbit couplings in the dynamics. Concerning the electronic structure calculations, we discuss the use of ab initio, density functional and semiempirical methods, and their combination with molecular mechanics (QM/MM approaches). Within the semiempirical framework, we provide a concise but updated description of our own method, based on configuration interaction with floating occupation molecular orbitals. We discuss the ability of different approaches to provide observables directly comparable with experimental results and to simulate a variety of photochemical and photophysical processes. In the concluding remarks, we stress how the border between direct and PES-fitting methods is not so sharp, and we briefly discuss recent trends that go beyond this traditional distinction

Photochemistry. A modern theoretical perspective

This book offers an introduction to photochemistry for students with a minimal background in physical chemistry and molecular quantum mechanics. The focus is from a theoretical perspective and highlights excited state dynamics. The authors, experienced lecturers, describe the main concepts in photochemical and photophysical processes that are used as a basis to interpret classical steady-state experimental results (essentially product branching ratios and quantum yields) and the most advanced time-resolved techniques. A significant portion of the content is devoted to the computational techniques present in quantum chemistry and molecular dynamics. With its short summaries, questions and exercises, this book is aimed at graduate students, while its theoretical focus differentiates it from most introductory textbooks on photochemistry

Improving Guess Geminals for the Geminal Mean Field Configuration Interaction Method

The purpose of this letter is to show that a rotation of Hartree-Fock canonical orbitals which minimizes the lowest eigenvalues of a configuration interaction calculation limited to the mono-excitated configurations from a given orbital allows one to construct a better starting guess for the geminal mean field configuration interaction method

Unveiling the photophysics of thiourea from CASPT2/CASSCF potential energy surfaces and singlet/triplet excited state molecular dynamics simulations

This work describes the decay mechanism of photoexcited thiourea, both in gas phase and in solution, from the information inferred from the topography of the excited and ground state potential energy surfaces and mixed singlet/triplet quantum classical molecular dynamics simulations. Our gas phase results reveal T1/S0 intersystem crossing as the dominant (49%) intrinsic decay channel to the ground state, which reaches a population of 0.28 at the final time of our simulations (10 ps). Population of the T1, would occur after internal conversion to the S1 from the spectroscopic S2 electronic state, followed by S1->T2 intersystem crossing and T2->T1 internal conversion processes. Minor decay channels occurring exclusively along the singlet manifold, i.e. S2->S0 (33%) and S1->S0 (18%), were also observed to play a role in the relaxation of photoexcited thiourea in the gas phase. The explicit incorporation of water-thiourea interactions in our simulations was found to provoke a very significant delay in the decay to the ground state of the system, with no transitions to the S0 being registered during the first 10 ps of our simulations. Intermolecular vibrational energy redistribution and explicit hydrogen bond interaction established between water molecules and the NH2 group of thiourea were found to structurally or energetically hamper the access to the intersystem crossing or internal conversion funnels with the ground state

The photo-orientation of azobenzene in viscous solutions, simulated by a stochastic model

We report a computational study of the photo-orientation kinetics in a viscous solution of azobenzene in ethylene glycol, under irradiation with linearly polarized light. The development of anisotropy and its interplay with photoisomerization are simulated by a stochastic model. A distinctive feature of the model is that it takes into account the photo-orientation angular distributions, specific for each isomer, obtained by nonadiabatic dynamics simulations at the molecular level. We find that the anisotropy, as measured by optical absorption dichroism, does not necessarily increase monotonously with time. As expected, the photo-orientation turns out to be strongly coupled with photoisomerization, but the latter is not a mandatory ingredient of this phenomenon: we predict that any chromophore undergoing large amplitude geometry relaxation during its excited state dynamics can develop anisotropy under suitable conditions

Surface hopping investigation of benzophenone excited state dynamics

We present a simulation of the photodynamics of benzophenone for the first 20 ps after n -> pi* excitation, performed by trajectory surface hopping calculations with on-the-fly semiempirical determination of potential energy surfaces and electronic wavefunctions. Both the dynamic and spin-orbit couplings are taken into account, and time-resolved fluorescence emission is also simulated. The computed decay time of the S-1 state is in agreement with experimental observations. The direct S-1 -> T-1 intersystem crossing (ISC) accounts for about 2/3 of the S-1 decay rate. The remaining 1/3 goes through T-2 or higher triplets. The nonadiabatic transitions within the triplet manifold are much faster than ISC and keep the population of T-1 at about 3/4 of the total triplet population, and that of the other states (mainly T-2) at 1/4. Two internal coordinates are vibrationally active immediately after n -> pi* excitation: one is the C-O stretching and the other one is a combination of the conrotatory torsion of phenyl rings and of bending involving the carbonyl C atom. The period of the torsion-bending mode coincides with oscillations in the time-resolved photoelectron spectra of Spighi et al. and substantially confirms their assignment

Dynamics of acetone photodissociation: a surface hopping study

We present on the fly surface hopping simulations of the dynamics of photoexcited acetone in the n->pi* band, taking into account both the spin-orbit and the dynamic couplings and allowing for the C-C bond dissociation. The S0, S1, T1 and T2 states were considered and the propagation time was 50 ps. According to the simulation results, after excitation to S1 both Internal Conversion (IC) to S0 and InterSystem Crossing (ISC) to T1 or T2 take place at comparable rates; T2 plays an important role and the simultaneous treatment of the spin-orbit and dynamic couplings is shown to be mandatory to describe the photodynamics. We propose a mechanism that explains the observed fast and slow decay rates of the S1 state of acetone

Nonadiabatic dynamics simulations of singlet fission in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene crystals

We present simulations of the singlet fission dynamics in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene (ThBF), a thienoquinoid compound recently investigated experimentally by Kawata et al. The simulation model consisted of two ThBF molecules embedded in their crystal environment. The aim was to understand the singlet fission mechanism, and to predict the excited state lifetimes and the singlet fission quantum yield, hitherto unknown. The simulations were performed by the trajectory surface hopping approach with on-the-fly calculations of the electronic wave functions and energies by the semiempirical FOMO-CI method. We found that the initially photogenerated excitonic bright state decays to the lower dark state with a biexponential behaviour, essentially due to transitions to other close lying states. The dark state in turn decays with a lifetime of about 1 ps to the double triplet 1TT state, which is long-lived, as ascertained by performing a simulation with inclusion of the spin-orbit coupling. The singlet fission quantum yield is predicted to be close to the theoretical maximum of 200%. In view of using this thienoquinoid compound in photovoltaic devices, a major drawback is the low energy of the T1 state at its equilibrium geometry

Interplay of radiative and nonradiative transitions in surface hopping with radiation-molecule interactions

We implemented a method for the treatment of field induced transitions in trajectory surface hopping simulations, in the framework of the local diabatization scheme, especially suited for on-the-fly dynamics. The method is applied to a simple one-dimensional model with an avoided crossing and compared with quantum wavepacket dynamics. The results show the importance of introducing a proper decoherence correction to surface hopping, in order to obtain meaningful results. Also the energy conservation policy of standard surface hopping must be revised: in fact, the quantum wavepacket energetics is well reproduced if energy absorption/emission is allowed for in the hops determined by radiation-molecule coupling. To our knowledge, this is the first time the issues of decoherence and energy conservation have been analyzed in depth to devise a mixed quantum-classical method for dynamics with molecule-field interactions

Energy Selection in Nonadiabatic Transitions

In this work we investigate whether and how a molecule undergoing a nonadiabatic transition can show different energy mean values and distributions in the two electronic states that are populated. We analyze three models, of which models I and II mimick the limiting cases of almost adiabatic and almost diabatic regimes, respectively, and are solvable by first-order perturbation theory. Model III represents realistically the photodissociation of a diatomic molecule and is treated numerically. The three models provide a consistent picture of the energy selection effect. For a typical avoided crossing, the wavepacket component that undegoes the transition between the two adiabatic states has a larger mean value of energy than the other component, both for upward and for downward transitions. The analysis of model II shows that the Landau-Zener rule can be deduced in a fully quantum mechanical way. We believe that the energy selection effect can be observed experimentally in the photodissociation of diatomic molecules. The effect should be particularly relevant for wavepackets endowed with a broad energy spectrum, as the result of excitation with ultrashort light pulses