Nonadiabatic coupling vectors for excited states within time-dependent density functional theory in the Tamm-Dancoff approximation and beyond

Recently, we have proposed a scheme for the calculation of nonadiabatic couplings and nonadiabatic coupling vectors within linear response time-dependent density functional theory using a set of auxiliary many-electron wavefunctions [ I. Tavernelli, E. Tapavicza, and U. Rothlisberger, J. Chem. Phys. 130, 124107 (2009) ]. As demonstrated in a later work [ I. Tavernelli, B. F. E. Curchod, and U. Rothlisberger, J. Chem. Phys. 131, 196101 (2009) ], this approach is rigorous in the case of the calculation of nonadiabatic couplings between the ground state and any excited state. In this work, we extend this formalism to the case of coupling between pairs of singly excited states with the same spin multiplicity. After proving the correctness of our formalism using the electronic oscillator approach by Mukamel and co-workers [ S. Tretiak and S. Mukamel, Chem. Rev. (Washington, D.C.) 102, 3171 (2002) ], we tested the method on a model system, namely, protonated formaldimine, for which we computed S1/S2 nonadiabatic coupling vectors and compared them with results from high level (MR-CISD) electronic structure calculations.

Position-Dependent Extension of π-Conjugation in D-π-A Dye Sensitizers and the Impact on the Charge-Transfer Properties

Thomas Wesley Holcombe, Jinhyun Kim, Jacques-Edouard Moser, Mateusz Barnaba Wielopolski, Yuxiang Yu, Shaik Mohammed Zakeeruddin

A series of five organic donor-π-bridge-acceptor (D-π-A) sensitizers is investigated within the context of their photoinduced charge-transfer properties. Thereby, the focus is set on the impact of structural modifications of the molecular architecture on the π-systems of the dyes. In particular, two different modes of systematic extension of the sensitizers’ π-systems, namely, (i) within the electron donating site and (ii) within the π-bridge, are investigated by means of steady-state and time-resolved spectroscopic methods. The photophysical studies of the molecules in solution and as deposited on Al2O3 or TiO2 films reveal that different effects on the charge-transfer characteristics evolve dependent where – within the molecular structure – the modification of the π-system is performed. Hence, π-extension of the donor sites, for instance, leads to a strong red shift of the absorption features and a variation of light-harvesting properties. Modifying the π-bridges results in a spatial decoupling of the HOMO and LUMO orbitals, which goes along with changes of the electronic coupling to TiO2. Furthermore, solution studies show that the electronic structure of the dyes governs their singlet excited-state features. As shown, the results obtained from these studies then allow important predictions about the deactivation of the excited states of these molecules adsorbed on TiO2. Finally, quantum chemical methods – among others, time-dependent density functional theory calculations – provide conclusive insight into the relationship between the electronic structure of the dyes and its impact on the photoinduced charge-transfer characteristics.

American Chemical Society2013

A Theoretical Rationalisation of the Emission Properties of Prototypical Cu(I)-Phenanthroline Complexes

Gloria Capano, Thomas James Penfold, Ursula Röthlisberger, Ivano Tavernelli

The excited state properties of transition metal complexes have become a central focus of research owing to a wide range of possible applications that seek to exploit their luminescence properties. Herein, we use density functional theory (DFT), time-dependent DFT (TDDFT), classical and quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations to provide a full understanding on the role of the geometric and electronic structure, spin orbit coupling, singlet triplet gap and the solvent environment on the emission properties of nine prototypical copper(I)-phenanthroline complexes. Our calculations reveal clear trends in the electronic properties that are strongly correlated to the luminescence properties, allowing us to rationalize the role of specific structural modifications. The MD simulations show, in agreement with recent experimental observations, that the lifetime shortening of the excited triplet state in donor solvents (acetonitrile) is not due to the formation of an exciplex. Instead, the solute solvent interaction is transient and arises from solvent structures that are similar to the ones already present in the ground state. These results based on a subset of the prototypical mononuclear Cu(I) complexes shed general insight into these complexes that may be exploited for development of mononuclear Cu(I) complexes for applications as, for example, emitters in third generation OLEDs.

2015

Investigations of the non-adiabatic photophysics of Cu(I)-phenanthroline complexes

Gloria Capano

Cu(I)-phenanthrolines are an important class of metal-organic molecules that exhibits much promise for solar energy harvesting and solar-driven catalysis applications. Although many experimental studies have been performed calling for high-level simulations to elucidate their photophysics, a complete picture is still missing. This is the goal of the present thesis. On the ultrafast (femtosecond) timescale we studied the non-adiabatic relaxation of a prototypical Cu(I)-phenanthroline, [Cu(dmp)2]+, by performing excited state simulations using two approaches: quantum dynamics and trajectory surface hopping. These simulations help to identify several mechanisms, internal conversion, pseudo Jahn-Teller distortion, intersystem crossing, occurring in the subpicosecond time scale. Surprisingly, we have found that intersystem crossing does not take place between the lowest singlet and triplet excited states, as previously proposed, but between the lowest singlet and higher triplet states. Moreover, we observed the initial stages (< 100 fs) of the solvent reorganization due to the electronic density changes in the excited state. This leads to an energy stabilization of the excited states that is associated with an increase of the non-radiative decay rate. The quantum dynamics simulations allowed us to provide indications for performing additional spectroscopy measurements by using the recently developed X-ray Free Electron Lasers (X-FELs). This technology can monitor both electronic and structural changes with an unprecedented time resolution of tens of femtoseconds and, therefore, is capable of revealing the aforementioned processes. In addition, we questioned the feasibility of such experiments and calculated the signal strengths for XAS and XES transient spectra. Finally, we analyzed the luminescence quenching, which has been observed for all Cu(I)-phenanthroline complexes when they are dissolved in strongly donating solvents. By performing Molecular Dynamics calculations we showed that, in contrast with the previously accepted model based on the formation of an exciplex (a species formed by two molecules, one in the excited state and one in the ground state), no stable exciplex is formed and that quenching is due to electrostatic solute-solvent interactions. In addition, we investigated how the geometry configuration can affect the luminescence lifetime in these molecules. We found a correlation between rigidity of the copper complex - inhibition of the pseudo Jahn-Teller distortion - and lifetime of the emission. The more the metal complex retains the ground state structure (large substituents), the longer its lifetime. This effect is attributed to a higher energy gap (excited state minus ground state energy) due to the reduction of relaxation. Our research reveals important insights into the relaxation mechanism and the complex interplay between geometry and electronic structure in Cu(I)-phenanthroline. These results can be exploited for guiding the synthesis of complexes with the desired physical properties.

EPFL2016

Investigations of the non-adiabatic photophysics of Cu(I)-phenanthroline complexes

Gloria Capano

EPFL2016