Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane

被引：14

作者：

Borne, Kurtis D. ^{[1
]}

Cooper, Joseph C. ^{[2
]}

Ashfold, Michael N. R. ^{[3
]}

Bachmann, Julien ^{[4
]}

Bhattacharyya, Surjendu ^{[1
]}

Boll, Rebecca ^{[5
]}

Bonanomi, Matteo ^{[6
,7
]}

Bosch, Michael ^{[4
]}

Callegari, Carlo ^{[8
]}

Centurion, Martin ^{[9
]}

Coreno, Marcello ^{[8
,10
]}

Curchod, Basile F. E. ^{[3
]}

Danailov, Miltcho B. ^{[8
]}

Demidovich, Alexander ^{[8
]}

Di Fraia, Michele ^{[8
]}

Erk, Benjamin ^{[11
]}

Facciala, Davide ^{[6
]}

Feifel, Raimund ^{[12
]}

Forbes, Ruaridh J. G. ^{[13
]}

Hansen, Christopher S. ^{[14
]}

Holland, David M. P. ^{[15
]}

Ingle, Rebecca A. ^{[16
]}

Lindh, Roland ^{[17
]}

Ma, Lingyu ^{[18
]}

Mcghee, Henry G. ^{[16
]}

Muvva, Sri Bhavya ^{[9
]}

Nunes, Joao Pedro Figueira ^{[9
]}

Odate, Asami ^{[18
]}

Pathak, Shashank ^{[1
]}

Plekan, Oksana ^{[8
]}

Prince, Kevin C. ^{[8
]}

Rebernik, Primoz ^{[8
]}

Rouzee, Arnaud ^{[19
]}

Rudenko, Artem ^{[1
]}

Simoncig, Alberto ^{[8
]}

Squibb, Richard J. ^{[12
]}

Venkatachalam, Anbu Selvam ^{[1
]}

Vozzi, Caterina ^{[6
]}

Weber, Peter M. ^{[18
]}

Kirrander, Adam ^{[2
]}

Rolles, Daniel ^{[1
]}

机构：

[1] Kansas State Univ, Dept Phys, JR Macdonald Lab, Manhattan, KS 66506 USA

[2] Univ Oxford, Dept Chem, Phys & Theoret Chem Lab, Oxford, England

[3] Univ Bristol, Sch Chem, Bristol, England

[4] Friedrich Alexander Univ Erlangen Nurnberg, Chem Thin Film Mat, Erlangen, Germany

[5] European XFEL, Schenefeld, Germany

[6] CNR, Ist Foton & Nanotecnol, IFN, Milan, Italy

[7] Politecn Milan, Dipartimento Fis, Milan, Italy

[8] Elettra Sincrotrone Trieste SCpA, Trieste, Italy

[9] Univ Nebraska Lincoln, Dept Phys & Astron, Lincoln, NE USA

[10] CNR, Ist Struttura Mat ISM, Trieste, Italy

[11] Deutsch Elektronen Synchrotron DESY, Hamburg, Germany

[12] Univ Gothenburg, Dept Phys, Gothenburg, Sweden

[13] SLAC Natl Accelerator Lab, Linac Coherent Light Source, Menlo Pk, CA USA

[14] Univ New South Wales, Sch Chem, Sydney, NSW, Australia

[15] Daresbury Lab, Warrington, England

[16] UCL, Dept Chem, London, England

[17] Uppsala Univ, Dept Chem BMC, Uppsala, Sweden

[18] Brown Univ, Dept Chem, Providence, RI USA

[19] Max Born Inst, Berlin, Germany

来源：

NATURE CHEMISTRY | 2024年 / 16卷 / 04期

基金：

英国工程与自然科学研究理事会; 澳大利亚研究理事会; 英国科学技术设施理事会; 瑞典研究理事会; 美国国家科学基金会; 欧盟地平线“2020”;

关键词：

DYNAMICS; ISOMERIZATION; PULSES;

D O I：

10.1038/s41557-023-01420-w

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

引用

页码：499 / 505

页数：16

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