Ultrafast X-ray scattering offers a structural view of excited-state charge transfer.
X-ray scattering
charge transfer
excited state
femtosecond
ultrafast dynamics
Journal
Proceedings of the National Academy of Sciences of the United States of America
ISSN: 1091-6490
Titre abrégé: Proc Natl Acad Sci U S A
Pays: United States
ID NLM: 7505876
Informations de publication
Date de publication:
11 05 2021
11 05 2021
Historique:
entrez:
5
5
2021
pubmed:
6
5
2021
medline:
6
5
2021
Statut:
ppublish
Résumé
Intramolecular charge transfer and the associated changes in molecular structure in N,N'-dimethylpiperazine are tracked using femtosecond gas-phase X-ray scattering. The molecules are optically excited to the 3p state at 200 nm. Following rapid relaxation to the 3s state, distinct charge-localized and charge-delocalized species related by charge transfer are observed. The experiment determines the molecular structure of the two species, with the redistribution of electron density accounted for by a scattering correction factor. The initially dominant charge-localized state has a weakened carbon-carbon bond and reorients one methyl group compared with the ground state. Subsequent charge transfer to the charge-delocalized state elongates the carbon-carbon bond further, creating an extended 1.634 Å bond, and also reorients the second methyl group. At the same time, the bond lengths between the nitrogen and the ring-carbon atoms contract from an average of 1.505 to 1.465 Å. The experiment determines the overall charge transfer time constant for approaching the equilibrium between charge-localized and charge-delocalized species to 3.0 ps.
Identifiants
pubmed: 33947814
pii: 2021714118
doi: 10.1073/pnas.2021714118
pmc: PMC8126834
pii:
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
Déclaration de conflit d'intérêts
The authors declare no competing interest.
Références
J Chem Phys. 2020 Feb 28;152(8):084307
pubmed: 32113333
J Phys Chem Lett. 2018 Nov 15;9(22):6556-6562
pubmed: 30380873
J Synchrotron Radiat. 2019 May 1;26(Pt 3):635-646
pubmed: 31074426
Nat Commun. 2019 Jul 18;10(1):3177
pubmed: 31320619
Angew Chem Int Ed Engl. 2000 Aug 4;39(15):2586-2631
pubmed: 10934390
Science. 2014 May 30;344(6187):1001-5
pubmed: 24876491
Science. 2015 Jan 9;347(6218):164-7
pubmed: 25574020
J Chem Theory Comput. 2019 May 14;15(5):2836-2846
pubmed: 30875212
Science. 2020 May 22;368(6493):885-889
pubmed: 32439793
J Chem Theory Comput. 2018 Jan 9;14(1):329-338
pubmed: 29140696
J Phys Condens Matter. 2010 Jun 30;22(25):253202
pubmed: 21393795
Angew Chem Int Ed Engl. 2019 May 6;58(19):6371-6375
pubmed: 30866169
Nature. 2020 Jun;582(7813):520-524
pubmed: 32581378
Nat Chem. 2019 Aug;11(8):716-721
pubmed: 31285542
Nat Commun. 2018 Dec 17;9(1):5348
pubmed: 30559404
Science. 1998 Jan 9;279(5348):202-5
pubmed: 9422687
J Chem Phys. 2008 Sep 14;129(10):104305
pubmed: 19044911
J Chem Theory Comput. 2019 Mar 12;15(3):1523-1537
pubmed: 30702882
Nat Commun. 2018 Nov 9;9(1):4733
pubmed: 30413712
Rev Sci Instrum. 2015 Jul;86(7):073702
pubmed: 26233391
Science. 2015 Nov 13;350(6262):790-5
pubmed: 26494175
Nat Commun. 2016 Mar 16;7:11013
pubmed: 26980327
Phys Rev Lett. 2015 Jun 26;114(25):255501
pubmed: 26197134
Nat Chem. 2019 Jun;11(6):504-509
pubmed: 30988415
Science. 2000 Aug 11;289(5481):935-8
pubmed: 10937993
Nature. 1992 Feb 27;355(6363):796-802
pubmed: 1311417
Nat Commun. 2020 Mar 6;11(1):1240
pubmed: 32144255
Science. 2014 Oct 17;346(6207):336-9
pubmed: 25324385
Rev Sci Instrum. 2014 Aug;85(8):083116
pubmed: 25173255
Science. 2018 Jul 6;361(6397):64-67
pubmed: 29976821
Struct Dyn. 2017 Dec 27;4(6):061508
pubmed: 29333473
Faraday Discuss. 2021 Feb 17;:
pubmed: 33595043
Sci Adv. 2019 Sep 06;5(9):eaax6625
pubmed: 31523713
Chem Soc Rev. 2013 Feb 21;42(4):1847-70
pubmed: 22850767
Phys Rev Lett. 2017 Feb 24;118(8):083001
pubmed: 28282194
J Chem Phys. 2013 Nov 21;139(19):194102
pubmed: 24320311
Struct Dyn. 2020 Jun 23;7(3):034102
pubmed: 32637459
Nat Commun. 2020 May 1;11(1):2157
pubmed: 32358535