54 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
Ultrafast Structural Dynamics of Photo-Reactions Revealed by Model-Independent X-ray Cross-Correlation Analysis
We applied angular X-ray Cross-Correlation analysis (XCCA) to scattering
images from a femtosecond resolution LCLS X-ray free-electron laser (XFEL)
pump-probe experiment with solvated PtPOP
([Pt(POH)]) metal complex molecules. The molecules
were pumped with linear polarized laser pulses creating an excited state
population with a preferred orientational (alignment) direction. Two time
scales of ps and ps were revealed by model-independent
XCCA, associated with an internal structural changes and rotational dephasing,
respectively. Our studies illustrate the potential of XCCA to reveal hidden
structural information in a model independent analysis of time evolution of
solvated metal complex molecules.Comment: 8 pages, 5 figures, 50 reference
The First Direct Detection of Kirkwood Transitions in Concentrated Aqueous Electrolytes using Small Angle X-ray Scattering
Ion-ion correlations, screening, and equilibrium bulk structure in various
concentrated electrolytes are investigated using synchrotron small angle X-ray
scattering (SAXS), theory, and molecular simulation. Utilizing SAXS
measurements we provide estimates of the Kirkwood Transition (KT) for a variety
of aqueous electrolytes (NaCl, CaCl, SrCl, and ErCl). The KT may be
defined as the concentration above which the ion-ion correlations cease to
decay exponentially with a single length scale given by the Debye length
and develop an additional length scale, that
reflects the formation of local domains of charge. Theoretical models of the KT
have been known for decades for highly idealized models of electrolytes, but
experimental verification of KT in real electrolytes has yet to be confirmed.
Herein, we provide consistent theoretical and experimental estimates of both
the inverse screening lengths and inverse domain size, for the
aforementioned electrolyte systems. Taken together, and are known
descriptors of the KT and provide a view into the complexity of ion-ion
interaction beyond the well-accepted Debye-H\"{u}ckel limit. Our findings
suggest a picture of interaction for real electrolytes that is more general
than that found in idealized models that is manifest in the precise form of the
non-local response function that we estimate through the interpretation of the
experimental SAXS signal. Importantly, the additional complexity of describing
ion-ion interaction of real electrolytes will implicate the short-range ion-ion
interactions that can only be computed via molecular simulation and provide a
quantitative approach to describe electrolyte phenomena beyond Debye-H\"{u}ckel
theory.Comment: 3
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