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Molecular dynamics of excited state intramolecular proton transfer: 3-hydroxyflavone in solution
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10.1063/1.4707736
/content/aip/journal/jcp/136/19/10.1063/1.4707736
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/19/10.1063/1.4707736

Figures

Image of FIG. 1.
FIG. 1.

Upon photoexcitation of the ground state normal form (top left), the excited state normal form (bottom left) undergoes proton transfer to yield the excited state tautomer form (bottom right) of 3-hydroxyflavone.

Image of FIG. 2.
FIG. 2.

(a) Upper panel: Normal form configuration of 3-HF showing the ground state dipole moment calculated from the ground state charge spline (orange arrow) and the excited state dipole moment calculated from the excited state charge spline (blue arrow). (b) Lower panel shows same results for the tautomer form.

Image of FIG. 3.
FIG. 3.

(a) Top left: Contour plot of the ground state DFT data of 3-HF with the stationary points (green) and intrinsic reaction path overlaid (white). (b) Top right: Contour plot of the EVB ground state of 3-HF with the DFT stationary points (green), EVB stationary points (yellow), and EVB intrinsic reaction path (blue) overlaid. (c) Bottom left: Contour plot of the excited state CIS data of 3-HF with the CIS stationary points (green) and CIS intrinsic reaction path overlaid (white). (d) Bottom right: Contour plot of the EVB excited state of 3-HF with the TDDFT stationary points (green), EVB stationary points (yellow), and EVB intrinsic reaction path (blue) overlaid.

Image of FIG. 4.
FIG. 4.

(a) Left panel: Time-dependent fluorescence Stokes shift of 3-HF in MCH with multi-exponential fit (red) overlaid. (b) Center panel: Time-dependent fluorescence Stokes shift of 3-HF in MeCN with multi-exponential fit (red) overlaid. (c) Right panel: Time-dependent fluorescence Stokes shift of 3-HF in MeOH with multi-exponential fit (red) overlaid.

Image of FIG. 5.
FIG. 5.

(a) Left panel: Proton transfer reaction time histogram of 3-HF in MCH. (b) Center panel: Proton transfer reaction time histogram of 3-HF in MeCN. (c) Right panel: Proton transfer reaction time histogram of 3-HF in MeOH.

Image of FIG. 6.
FIG. 6.

(a) Left panel: Fluorescence spectrum of 3-HF in MCH solvent after 10 ps of simulation time. (b) Center panel: Fluorescence spectrum of 3-HF in MeCN solvent after 10 ps of simulation time. (c) Right panel: Fluorescence spectrum of 3-HF in MeOH solvent after 10 ps of simulation time.

Image of FIG. 7.
FIG. 7.

Potential energy along the intrinsic reaction path projected onto the proton transfer coordinate for the ground electronic state (blue curve) and the excited electronic state (green curve). The red arrow marks the vertical transition from the ground state normal form (blue dot) to the excited state potential energy wall, roughly 3 kcal/mol above the excited state normal form (green dot).

Image of FIG. 8.
FIG. 8.

(a) Left panel: Initial positions of the ultrafast trajectories on the excited state EVB potential energy surface. (b) Right panel: Initial positions of the slow trajectories on the excited state EVB potential energy surface. These panels report results for MeOH solvent.

Image of FIG. 9.
FIG. 9.

Trajectories of various bond distances between the transferring proton on 3-HF and the O-atom on the blocking methanol to which it is initially intermolecularly H-bonded (blue curve); the O-atom on the mediator methanol molecule that approaches from solution and disrupts the blocking H-bond (green curve); and the tautomer form intramolecular O-atom on 3-HF (red curve) to which the transferring proton first H-bonds (around 8 ps) and then transfers to (beyond 9 ps).

Image of FIG. 10.
FIG. 10.

(a) Left panel: Stokes shift residual time series of 3-HF in MCH. (b) Center panel: Stokes shift residual time series of 3-HF in MeCN. (c) Right panel: Stokes shift residual time series of 3-HF in MeOH.

Image of FIG. 11.
FIG. 11.

Fourier transforms of the Stokes shift residual time series presented in Fig. 10. (a) Left panel: Vibrational frequency spectrum of 3-HF in MCH solvent. (b) Center panel: Vibrational frequency spectrum of 3-HF in MeCN solvent. (c) Right panel: Vibrational frequency spectrum of 3-HF in MeOH solvent.

Image of FIG. 12.
FIG. 12.

From the top: (a) Phenyl out of plane bend promoting mode present in MeOH solvent; (b) carbon–carbon deformation promoting mode present in MeCN and MeOH solvents; (c) oxygen–oxygen in plane bend promoting mode present in all three solvents; (d) carbon–hydrogen out of plane bend promoting mode present in all three solvents; and (e) carbon–oxygen–carbon stretch promoting mode present in MeOH solvent.

Image of FIG. 13.
FIG. 13.

Upper panels give vibrational frequency spectra of 3-HF calculated for ultrafast reacting trajectories in (left to right): (a) MCH solvent; (b) MeCN solvent; and (c) MeOH. Lower panels give slow vibrational frequency spectrum of 3-HF calculated for slow reacting trajectories in (left to right): (d) MCH solvent; (e) MeCN solvent; and (f) MeOH solvent.

Tables

Generic image for table
Table I.

Relative barrier heights (kcal/mol) of the DFT ground state and EVB ground state of 3-HF.

Generic image for table
Table II.

Relative barrier heights (kcal/mol) of the TDDFT excited state and EVB excited state of 3-HF.

Generic image for table
Table III.

Comparison of the ESIPT kinetics determined from molecular dynamics simulations to those determined from experiment.

Generic image for table
Table IV.

Assignments of vibrational peaks obtained from the Fourier analysis of residual Stokes shift correlation function to intramolecular normal mode vibrations. (a) MCH solvent, (b) MeCN solvent, and (c) MeOH solvent.

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/content/aip/journal/jcp/136/19/10.1063/1.4707736
2012-05-18
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Molecular dynamics of excited state intramolecular proton transfer: 3-hydroxyflavone in solution
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/19/10.1063/1.4707736
10.1063/1.4707736
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