Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

Kristjan Kunnus; Morgane Vacher; Tobias C. B. Harlang; Kasper Skov Kjær; Kristoffer Haldrup; Elisa Biasin; Tim B. van Driel; Mátyás Imre Pápai; Pavel Chabera; Yizhu Liu; Hideyuki Tatsuno; Cornelia Timm; Erik Källman; Mickaël Delcey; Robert W. Hartsock; Marco E. Reinhard; Sergey Koroidov; Mads  Laursen; Frederik B. Hansen; Peter Vester; Morten Christensen; Lise Sandberg; Zoltán Németh; Dorottya Sárosiné Szemes; Éva Bajnóczi; Roberto Alonso-Mori; James M. Glownia; Silke Nelson; Marcin Sikorski; Dimosthenis Sokaras; Henrik T. Lemke; Sophie E. Canton; Klaus  Braagaard Møller; Martin Meedom Nielsen; György Vankó; Kenneth Wärnmark; Villy Sundström; Petter Persson; Marcus Lundberg; Jens Uhlig; Kelly J. Gaffney

doi:10.1038/s41467-020-14468-w

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

Kristjan Kunnus^*, Morgane Vacher, Tobias C. B. Harlang, Kasper Skov Kjær, Kristoffer Haldrup, Elisa Biasin, Tim B. van Driel, Mátyás Imre Pápai, Pavel Chabera, Yizhu Liu, Hideyuki Tatsuno, Cornelia Timm, Erik Källman, Mickaël Delcey, Robert W. Hartsock, Marco E. Reinhard, Sergey Koroidov, Mads Laursen, Frederik B. Hansen, Peter VesterMorten Christensen, Lise Sandberg, Zoltán Németh, Dorottya Sárosiné Szemes, Éva Bajnóczi, Roberto Alonso-Mori, James M. Glownia, Silke Nelson, Marcin Sikorski, Dimosthenis Sokaras, Henrik T. Lemke, Sophie E. Canton, Klaus Braagaard Møller, Martin Meedom Nielsen, György Vankó, Kenneth Wärnmark, Villy Sundström, Petter Persson, Marcus Lundberg, Jens Uhlig, Kelly J. Gaffney

^*Corresponding author for this work

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Abstract

The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)₂]²⁺ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (³MC) excited state surface. This ³MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a ³MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.

Original language	English
Article number	634
Journal	Nature Communications
Volume	11
Issue number	1
Number of pages	11
ISSN	2041-1723
DOIs	https://doi.org/10.1038/s41467-020-14468-w
Publication status	Published - 2020

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Kunnus, K., Vacher, M., Harlang, T. C. B., Kjær, K. S., Haldrup, K., Biasin, E., van Driel, T. B., Pápai, M. I., Chabera, P., Liu, Y., Tatsuno, H., Timm, C., Källman, E., Delcey, M., Hartsock, R. W., Reinhard, M. E., Koroidov, S., Laursen, M., Hansen, F. B., ... Gaffney, K. J. (2020). Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering. Nature Communications, 11(1), Article 634. https://doi.org/10.1038/s41467-020-14468-w

@article{16d953775b884e7f9808888b801caacb,

title = "Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering",

abstract = "The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. This 3MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.",

author = "Kristjan Kunnus and Morgane Vacher and Harlang, {Tobias C. B.} and Kj{\ae}r, {Kasper Skov} and Kristoffer Haldrup and Elisa Biasin and {van Driel}, {Tim B.} and P{\'a}pai, {M{\'a}ty{\'a}s Imre} and Pavel Chabera and Yizhu Liu and Hideyuki Tatsuno and Cornelia Timm and Erik K{\"a}llman and Micka{\"e}l Delcey and Hartsock, {Robert W.} and Reinhard, {Marco E.} and Sergey Koroidov and Mads Laursen and Hansen, {Frederik B.} and Peter Vester and Morten Christensen and Lise Sandberg and Zolt{\'a}n N{\'e}meth and Szemes, {Dorottya S{\'a}rosin{\'e}} and {\'E}va Bajn{\'o}czi and Roberto Alonso-Mori and Glownia, {James M.} and Silke Nelson and Marcin Sikorski and Dimosthenis Sokaras and Lemke, {Henrik T.} and Canton, {Sophie E.} and {Braagaard M{\o}ller}, Klaus and Nielsen, {Martin Meedom} and Gy{\"o}rgy Vank{\'o} and Kenneth W{\"a}rnmark and Villy Sundstr{\"o}m and Petter Persson and Marcus Lundberg and Jens Uhlig and Gaffney, {Kelly J.}",

year = "2020",

doi = "10.1038/s41467-020-14468-w",

language = "English",

volume = "11",

journal = "Nature Communications",

issn = "2041-1723",

publisher = "Nature Research",

number = "1",

}

Kunnus, K, Vacher, M, Harlang, TCB, Kjær, KS, Haldrup, K, Biasin, E, van Driel, TB, Pápai, MI, Chabera, P, Liu, Y, Tatsuno, H, Timm, C, Källman, E, Delcey, M, Hartsock, RW, Reinhard, ME, Koroidov, S, Laursen, M, Hansen, FB, Vester, P, Christensen, M, Sandberg, L, Németh, Z, Szemes, DS, Bajnóczi, É, Alonso-Mori, R, Glownia, JM, Nelson, S, Sikorski, M, Sokaras, D, Lemke, HT, Canton, SE, Braagaard Møller, K , Nielsen, MM, Vankó, G, Wärnmark, K, Sundström, V, Persson, P, Lundberg, M, Uhlig, J & Gaffney, KJ 2020, 'Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering', Nature Communications, vol. 11, no. 1, 634. https://doi.org/10.1038/s41467-020-14468-w

TY - JOUR

T1 - Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

AU - Kunnus, Kristjan

AU - Vacher, Morgane

AU - Harlang, Tobias C. B.

AU - Kjær, Kasper Skov

AU - Haldrup, Kristoffer

AU - Biasin, Elisa

AU - van Driel, Tim B.

AU - Pápai, Mátyás Imre

AU - Chabera, Pavel

AU - Liu, Yizhu

AU - Tatsuno, Hideyuki

AU - Timm, Cornelia

AU - Källman, Erik

AU - Delcey, Mickaël

AU - Hartsock, Robert W.

AU - Reinhard, Marco E.

AU - Koroidov, Sergey

AU - Laursen, Mads

AU - Hansen, Frederik B.

AU - Vester, Peter

AU - Christensen, Morten

AU - Sandberg, Lise

AU - Németh, Zoltán

AU - Szemes, Dorottya Sárosiné

AU - Bajnóczi, Éva

AU - Alonso-Mori, Roberto

AU - Glownia, James M.

AU - Nelson, Silke

AU - Sikorski, Marcin

AU - Sokaras, Dimosthenis

AU - Lemke, Henrik T.

AU - Canton, Sophie E.

AU - Braagaard Møller, Klaus

AU - Nielsen, Martin Meedom

AU - Vankó, György

AU - Wärnmark, Kenneth

AU - Sundström, Villy

AU - Persson, Petter

AU - Lundberg, Marcus

AU - Uhlig, Jens

AU - Gaffney, Kelly J.

PY - 2020

Y1 - 2020

N2 - The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. This 3MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.

AB - The non-equilibrium dynamics of electrons and nuclei govern the function of photoactive materials. Disentangling these dynamics remains a critical goal for understanding photoactive materials. Here we investigate the photoinduced dynamics of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS). This measurement shows temporal oscillations in the XES and XSS difference signals with the same 278 fs period oscillation. These oscillations originate from an Fe-ligand stretching vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. This 3MC state is populated with a 110 fs time constant by 40% of the excited molecules while the rest relax to a 3MLCT excited state. The sensitivity of the Kα XES to molecular structure results from a 0.7% average Fe-ligand bond length shift between the 1 s and 2p core-ionized states surfaces.

U2 - 10.1038/s41467-020-14468-w

DO - 10.1038/s41467-020-14468-w

M3 - Journal article

C2 - 32005815

AN - SCOPUS:85078841027

SN - 2041-1723

VL - 11

JO - Nature Communications

JF - Nature Communications

IS - 1

M1 - 634

ER -

Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

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