Observation of the molecular response to light upon photoexcitation.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
01 05 2020
01 05 2020
Historique:
received:
06
01
2020
accepted:
23
03
2020
entrez:
3
5
2020
pubmed:
3
5
2020
medline:
3
5
2020
Statut:
epublish
Résumé
When a molecule interacts with light, its electrons can absorb energy from the electromagnetic field by rapidly rearranging their positions. This constitutes the first step of photochemical and photophysical processes that include primary events in human vision and photosynthesis. Here, we report the direct measurement of the initial redistribution of electron density when the molecule 1,3-cyclohexadiene (CHD) is optically excited. Our experiments exploit the intense, ultrashort hard x-ray pulses of the Linac Coherent Light Source (LCLS) to map the change in electron density using ultrafast x-ray scattering. The nature of the excited electronic state is identified with excellent spatial resolution and in good agreement with theoretical predictions. The excited state electron density distributions are thus amenable to direct experimental observation.
Identifiants
pubmed: 32358535
doi: 10.1038/s41467-020-15680-4
pii: 10.1038/s41467-020-15680-4
pmc: PMC7195484
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Langues
eng
Sous-ensembles de citation
IM
Pagination
2157Références
Zhang, W. et al. Tracking excited-state charge and spin dynamics in iron coordination complexes. Nature 509, 345–348 (2014).
pubmed: 24805234
pmcid: 24805234
doi: 10.1038/nature13252
Minitti, M. P. et al. Imaging molecular motion: femtosecond x-ray scattering of an electrocyclic chemical reaction. Phys. Rev. Lett. 114, 255501 (2015).
pubmed: 26197134
doi: 10.1103/PhysRevLett.114.255501
Kim, K. H. et al. Direct observation of bond formation in solution with femtosecond X-ray scattering. Nature 518, 385–389 (2015).
pubmed: 25693570
doi: 10.1038/nature14163
Wernet, P. et al. Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)
pubmed: 25832405
doi: 10.1038/nature14296
Pande, K. et al. Femtosecond structural dynamics drives the trans/cis isomerization in photoactive yellow protein. Science 352, 725–729 (2016).
pubmed: 27151871
pmcid: 5291079
doi: 10.1126/science.aad5081
Öström, H. et al. Probing the transition state region in catalytic CO oxidation on Ru. Science 347, 978–982 (2015).
pubmed: 25722407
doi: 10.1126/science.1261747
Rudenko, A. et al. Femtosecond response of polyatomic molecules to ultra-intense hard X-rays. Nature 546, 129–132 (2017).
pubmed: 28569799
doi: 10.1038/nature22373
Stankus, B. et al. Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation. Nat. Chem. 11, 716–721 (2019).
pubmed: 31285542
doi: 10.1038/s41557-019-0291-0
Ischenko, A. A., Weber, P. M. & Dwayne Miller, R. J. Capturing chemistry in action with electrons: realization of atomically resolved reaction dynamics. Chem. Rev. 117, 11066–11124 (2017).
pubmed: 28590727
doi: 10.1021/acs.chemrev.6b00770
Ben-Nun, M., Martínez, T. J., Weber, P. M. & Wilson, K. R. Direct imaging of excited electronic states using diffraction techniques: theoretical considerations. Chem. Phys. Lett. 262, 405–414 (1996).
doi: 10.1016/0009-2614(96)01108-6
Debnarova, A., Techert, S. & Schmatz, S. Ab initio studies of ultrafast x-ray scattering of the photodissociation of iodine. J. Chem. Phys. 133, 124309 (2010).
pubmed: 20886934
doi: 10.1063/1.3475567
Kirrander, A. X-ray diffraction assisted spectroscopy of Rydberg states. J. Chem. Phys. 137, 154310 (2012).
pubmed: 23083168
doi: 10.1063/1.4757913
Parrish, R. M. & Martínez, T. J. Ab initio computation of rotationally-averaged pump-probe x-ray and electron diffraction signals. J. Chem. Theory Comput. 15, 1523–1537 (2019).
pubmed: 30702882
doi: 10.1021/acs.jctc.8b01051
Stolow, A. The Three pillars of photo-initiated quantum molecular dynamics. Faraday Discuss. 163, 9–32 (2013).
pubmed: 24020194
doi: 10.1039/c3fd90021e
Attar, A. R. et al. Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction. Science 356, 54–59 (2017).
pubmed: 28386006
doi: 10.1126/science.aaj2198
Li, W. et al. Visualizing electron rearrangement in space and time during the transition from a molecule to atoms. PNAS 107, 20219–20222 (2010).
pubmed: 21059945
doi: 10.1073/pnas.1014723107
Adachi, S., Sato, M. & Suzuki, T. Direct observation of ground-state product formation in a 1,3-cyclohexadiene ring-opening reaction. J. Phys. Chem. Lett. 6, 343–346 (2015).
pubmed: 26261944
doi: 10.1021/jz502487r
Gessner, O. et al. Femtosecond multidimensional imaging of a molecular dissociation. Science 311, 219–222 (2006).
pubmed: 16357226
doi: 10.1126/science.1120779
Yong, H. et al. Determining orientations of optical transition dipole moments using ultrafast x-ray scattering. J. Phys. Chem. Lett. 9, 6556–6562 (2018).
pubmed: 30380873
doi: 10.1021/acs.jpclett.8b02773
pmcid: 30380873
Pressprich, M. R., White, M. A. & Coppens, P. Single-crystal x-ray analysis of an electronic excited state: the structure determination of a metastable state of sodium nitroprusside. J. Am. Chem. Soc. 115, 6444–6445 (1993).
doi: 10.1021/ja00067a083
Kim, C. D., Pillet, S., Wu, G., Fullagar, W. K. & Coppens, P. Excited-state structure by time-resolved X-ray diffraction. Acta Cryst. A 58, 133–137 (2002).
doi: 10.1107/S0108767301017986
Biasin, E. et al. Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [Co(terpy)2]2
pubmed: 27419566
doi: 10.1103/PhysRevLett.117.013002
Deb, S. & Weber, P. M. The ultrafast pathway of photon-induced electrocyclic ring-opening reactions: the case of 1,3-cyclohexadiene. Annu. Rev. Phys. Chem. 62, 19–39 (2011).
pubmed: 21054174
doi: 10.1146/annurev.physchem.012809.103350
Wolf, T. J. A. et al. The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction. Nat. Chem. 11, 504–509 (2019).
pubmed: 30988415
doi: 10.1038/s41557-019-0252-7
Pemberton, C. C., Zhang, Y., Salta, K., Kirrander, A. & Weber, P. M. From the (1B) spectroscopic state to the photochemical product of the ultrafast ring-opening of 1,3-cyclohexadiene: a spectral observation of the complete reaction path. J. Phys. Chem. A 119, 8832–8845 (2015).
pubmed: 26192201
doi: 10.1021/acs.jpca.5b05672
Merchán, M. et al. Electronic spectra of 1,4-cyclohexadiene and 1,3-cyclohexadiene: a combined experimental and theoretical investigation. J. Phys. Chem. A 103, 5468–5476 (1999).
doi: 10.1021/jp991266z
Bühler, C. C., Minitti, M. P., Deb, S., Bao, J. & Weber, P. M. Ultrafast dynamics of 1,3-cyclohexadiene in highly excited states. J. Atom. Mol. Phys. 2011, 637593 (2011).
Emma, P. et al. First lasing and operation of an Ångström-wavelength free-electron laser. Nat. Photonics 4, 641–647 (2010).
doi: 10.1038/nphoton.2010.176
Lorenz, U., Møller, K. B. & Henriksen, N. E. On the interpretation of time-resolved anisotropic diffraction patterns. New J. Phys. 12, 113022 (2010).
doi: 10.1088/1367-2630/12/11/113022
Budarz, J. M. et al. Observation of femtosecond molecular dynamics via pump-probe gas phase x-ray scattering. J. Phys. B. Mol. Opt. Phys. 49, 034001 (2016).
doi: 10.1088/0953-4075/49/3/034001
Northey, T., Zotev, N. & Kirrander, A. Ab initio calculation of molecular diffraction. J. Chem. Theory Comput. 10, 4911–4920 (2014).
pubmed: 26584376
doi: 10.1021/ct500096r
Northey, T., Carrascosa, A. M., Schäfer, S. & Kirrander, A. Elastic x-ray scattering from state-selected molecules. J. Chem. Phys. 145, 154304 (2016).
pubmed: 27782487
doi: 10.1063/1.4962256
Ruddock, J. M. et al. Simplicity beneath complexity: counting molecular electrons reveals transients and kinetics of photodissociation reactions. Angew. Chem. Int. Ed. 58, 6371–6375 (2019).
doi: 10.1002/anie.201902228
Halavanau, A., Decker, F.-J., Emma, C., Sheppard, J. & Pellegrini, C. Very high brightness and power LCLS-II hard X-ray pulses. J. Synchrotron Radiat. 26, 635–646 (2019).
pubmed: 31074426
doi: 10.1107/S1600577519002492
Carrascosa, A. M., Yong, H., Crittenden, D. L., Weber, P. M. & Kirrander, A. Ab initio calculation of total x-ray scattering from molecules. J. Chem. Theory Comput. 15, 2836–2846 (2019).
doi: 10.1021/acs.jctc.9b00056
Yong, H. et al. Scattering off molecules far from equilibrium. J. Chem. Phys. 151, 084301 (2019).
pubmed: 31470697
doi: 10.1063/1.5111979
Grabowsky, S., Genoni, A. & Bürgi, H.-B. Quantum crystallography. Chem. Sci. 8, 4159–4176 (2017).
pubmed: 28878872
pmcid: 5576428
doi: 10.1039/C6SC05504D
Liang, M. et al. The coherent X-ray imaging instrument at the Linac Coherent Light Source. J. Synchrotron Radiat. 22, 514–519 (2015).
pubmed: 25931062
pmcid: 4416669
doi: 10.1107/S160057751500449X
Kaufmann, K., Baumeister, W. & Jungen, M. Universal gaussian basis sets for an optimum representation of Rydberg and continuum wavefunctions. J. Phys. B. Mol. Opt. Phys. 22, 2223–2240 (1989).
doi: 10.1088/0953-4075/22/14/007
Werner, H. J., Knowles, P. J., Knizia, G., Manby, F. R. & Schütz, M. Molpro: a general-purpose quantum chemistry program package. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2, 242–253 (2012).
doi: 10.1002/wcms.82
Zotev, N. et al. Excited electronic states in total isotropic scattering from molecules. J. Chem. Theory Comp. 16, 2594–2605 (2020).
doi: 10.1021/acs.jctc.9b00670
Prince, E. International Tables for Crystallography. Mathematical, Physical and Chemical Tables 3rd edn, Vol. C (Springer, Dordrecht, 2006).