39 research outputs found
On the interplay of solvent and conformational effects in simulated excited-state dynamics of a copper phenanthroline photosensitizer
Post-print (lokagerð höfundar)Copper(I) bis-phenanthroline complexes represent Earth-abundant alternatives to ruthenium-based sensitizers for solar energy conversion and photocatalysis. Improved understanding of the solvent- mediated excited-state structural dynamics can help optimize their photoconversion efficiency. Through direct dynamics simulations in acetonitrile and excited-state minimum energy path calculations in vacuum, we uncover the mechanism of the photoinduced flattening motion of the prototypical system [Cu(dmphen)2]+ (dmphen = 2,9-dimethyl-1,10-phenanthroline). We find that the ligand distortion is a two-step process in acetonitrile. The fast component (~110 fs) is due to spontaneous pseudo Jahn– Teller instability and is largely solvent independent, while the slow component (~1.2 ps) arises from the mutual interplay between solvent molecules closely approaching the metal center and rotation of the methyl substituents. These results shed new light on the influence of a donor solvent such as acetonitrile and methyl substituents on the flattening dynamics of [Cu(dmphen)2]+.The present work has received funding from the Icelandic
Research Fund (grants number 196070-051 and 196279-051). The authors are grateful to Aleksei Ivanov for support with the
NEB calculations and Ask H. Larsen for discussion about the
implementation of the acetonitrile force field in ASE.Peer Reviewe
Anisotropy enhanced X-ray scattering from solvated transition metal complexes
Time-resolved X-ray scattering patterns from photoexcited molecules in
solution are in many cases anisotropic at the ultrafast time scales accessible
at X-ray Free Electron Lasers (XFELs). This anisotropy arises from the
interaction of a linearly polarized UV-vis pump laser pulse with the sample,
which induces anisotropic structural changes that can be captured by
femtosecond X-ray pulses. In this work we describe a method for quantitative
analysis of the anisotropic scattering signal arising from an ensemble of
molecules and we demonstrate how its use can enhance the structural sensitivity
of the time-resolved X-ray scattering experiment. We apply this method on
time-resolved X-ray scattering patterns measured upon photoexcitation of a
solvated di-platinum complex at an XFEL and explore the key parameters
involved. We show that a combined analysis of the anisotropic and isotropic
difference scattering signals in this experiment allows a more precise
determination of the main photoinduced structural change in the solute, i.e.
the change in Pt-Pt bond length, and yields more information on the excitation
channels than the analysis of the isotropic scattering only. Finally, we
discuss how the anisotropic transient response of the solvent can enable the
determination of key experimental parameters such as the Instrument Response
Function.Comment: Accepted for publication in Journal of Synchrotron Radiatio
Atomistic characterization of the active-site solvation dynamics of a model photocatalyst
The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2 (dimen) 4 ] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution function, enabling the solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis
Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy
Light-driven molecular reactions are dictated by the excited state potential energy landscape, depending critically on the location of conical intersections and intersystem crossing points between potential surfaces where non-adiabatic effects govern transition probabilities between distinct electronic states. While ultrafast studies have provided significant insight into electronic excited state reaction dynamics, experimental approaches for identifying and characterizing intersections and seams between electronic states remain highly system dependent. Here we show that for 3d transition metal systems simultaneously recorded X-ray diffuse scattering and X-ray emission spectroscopy at sub-70 femtosecond time-resolution provide a solid experimental foundation for determining the mechanistic details of excited state reactions. In modeling the mechanistic information retrieved from such experiments, it becomes possible to identify the dominant trajectory followed during the excited state cascade and to determine the relevant loci of intersections between states. We illustrate our approach by explicitly mapping parts of the potential energy landscape dictating the light driven low-to-high spin-state transition (spin crossover) of [Fe(2,2′-bipyridine)3]2+, where the strongly coupled nuclear and electronic dynamics have been a source of interest and controversy. We anticipate that simultaneous X-ray diffuse scattering and X-ray emission spectroscopy will provide a valuable approach for mapping the reactive trajectories of light-triggered molecular systems involving 3d transition metals
Solution Structure and Ultrafast Vibrational Relaxation of the PtPOP Complex Revealed by ΔSCF-QM/MM Direct Dynamics Simulations
Recent
ultrafast experiments have unveiled the time scales of vibrational
cooling and decoherence upon photoexcitation of the diplatinum complex
[Pt<sub>2</sub>(P<sub>2</sub>O<sub>5</sub>H<sub>2</sub>)<sub>4</sub>]<sup>4–</sup> in solvents. Here, we contribute to the understanding
of the structure and dynamics of the lowest lying singlet excited
state of the model photocatalyst by performing potential energy surface
calculations and Born–Oppenheimer molecular dynamics simulations
in the gas phase and in water. Solvent effects were treated using
a multiscale quantum mechanics/molecular mechanics approach. Fast
sampling was achieved with a modified version of delta self-consistent
field implemented in the grid-based projector-augmented wave density
functional theory code. The known structural parameters and the PESs
of the first singlet and triplet excited states are correctly reproduced.
Besides, the simulations deliver clear evidence that pseudorotation
of the ligands in the excited state leads to symmetry lowering of
the Pt<sub>2</sub>P<sub>8</sub> core. Coherence decay of Pt–Pt
stretching vibrations in solution was found to be governed by vibrational
cooling, which is in agreement with previous ultrafast experiments.
We also show that the flow of excess Pt–Pt vibrational energy
is first directed toward vibrational modes involving the ligands,
with the solvent favoring intramolecular vibrational energy redistribution.
The results are supported by thorough vibrational analysis in terms
of generalized normal modes