Sökning: id:"swepub:oai:DiVA.org:kth-311201" >
Breaking inversion ...
Breaking inversion symmetry by protonation : Experimental and theoretical NEXAFS study of the diazynium ion, N2H
-
- Couto, Rafael Carvalho (författare)
- KTH Royal Institute of Technology,KTH,Teoretisk kemi och biologi,Royal Inst Technol, Sch Chem Biotechnol & Hlth, Dept Theoret Chem & Biol, SE-10691 Stockholm, Sweden.;Stockholm Univ, Albanova Univ Ctr, Dept Phys, SE-10691 Stockholm, Sweden.
-
- Hua, W. (författare)
- Nanjing Univ Sci & Technol, Sch Sci, Dept Appl Phys, MIIT Key Lab Semicond Microstruct & Quantum Sensi, Nanjing 210094, Peoples R China.,Nanjing University of Science and Technology
-
- Lindblad, Rebecka, Dr, 1984- (författare)
- Uppsala University,Lund University,Lunds universitet,Uppsala universitet,Oorganisk kemi,Lund Univ, Dept Phys, Box 118, S-22100 Lund, Sweden.;Helmholtz Zentrum Berlin Mat & Energie, Abt Hochempfindliche Rontgenspektroskopie, Albert Einstein Str 15, D-12489 Berlin, Germany.,Synkrotronljusfysik,Fysiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Synchrotron Radiation Research,Department of Physics,Departments at LTH,Faculty of Engineering, LTH,Helmholtz-Zentrum Berlin für Materialien und Energie GmbH
-
visa fler...
-
- Kjellsson, Ludvig (författare)
- Uppsala University,Uppsala universitet,Institutionen för fysik och astronomi,European XFEL GmbH, Holzkoppel 4, D-22869 Schenefeld, Germany.,Röntgenfysik
-
- Sorensen, Stacey L. (författare)
- Lund University,Lunds universitet,Synkrotronljusfysik,Fysiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Synchrotron Radiation Research,Department of Physics,Departments at LTH,Faculty of Engineering, LTH
-
- Kubin, M. (författare)
- Helmholtz Zentrum Berlin Mat & Energie, Abt Hochempfindliche Rontgenspektroskopie, Albert Einstein Str 15, D-12489 Berlin, Germany.,Helmholtz Association of German Research Centers
-
- Bülow, C. (författare)
- Helmholtz Zentrum Berlin Mat & Energie, Abt Hochempfindliche Rontgenspektroskopie, Albert Einstein Str 15, D-12489 Berlin, Germany.,Helmholtz Association of German Research Centers
-
- Timm, M. (författare)
- Helmholtz Zentrum Berlin Mat & Energie, Abt Hochempfindliche Rontgenspektroskopie, Albert Einstein Str 15, D-12489 Berlin, Germany.,Helmholtz Association of German Research Centers
-
- Zamudio-Bayer, V. (författare)
- Helmholtz Zentrum Berlin Mat & Energie, Abt Hochempfindliche Rontgenspektroskopie, Albert Einstein Str 15, D-12489 Berlin, Germany.,Helmholtz Association of German Research Centers
-
- Von Issendorff, B. (författare)
- Albert Ludwigs Univ Freiburg, Phys Inst, Hermann Herder Str 3, D-79104 Freiburg, Germany.,Albert-Ludwigs University Freiburg
-
- Söderström, Johan, 1978- (författare)
- Uppsala University,Uppsala universitet,Kemisk och biomolekylär fysik
-
- Lau, J. T. (författare)
- Helmholtz Zentrum Berlin Mat & Energie, Abt Hochempfindliche Rontgenspektroskopie, Albert Einstein Str 15, D-12489 Berlin, Germany.;Albert Ludwigs Univ Freiburg, Phys Inst, Hermann Herder Str 3, D-79104 Freiburg, Germany.,Helmholtz Association of German Research Centers,Albert-Ludwigs University Freiburg
-
- Rubensson, Jan-Erik (författare)
- Uppsala University,Uppsala universitet,Kemisk och biomolekylär fysik
-
- Ågren, Hans (författare)
- Uppsala University,Uppsala universitet,Institutionen för fysik och astronomi,Tomsk State Univ, 36 Lenin Ave, Tomsk, Russia.,Röntgenfysik,Tomsk State University
-
- Carravetta, V. (författare)
- CNR, IPCF, Via Moruzzi 1, I-56124 Pisa, Italy.,CNR Istituto per le Tecnologie Applicate ai Beni Culturali (CNR-ITABC)
-
visa färre...
-
(creator_code:org_t)
- 2021
- 2021
- Engelska.
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 23:32, s. 17166-17176
- Relaterad länk:
-
https://doi.org/10.1...
-
visa fler...
-
https://pubs.rsc.org...
-
https://uu.diva-port... (primary) (Raw object)
-
http://dx.doi.org/10... (free)
-
https://urn.kb.se/re...
-
https://doi.org/10.1...
-
https://urn.kb.se/re...
-
https://lup.lub.lu.s...
-
visa färre...
Abstract
Ämnesord
Stäng
- As an example of symmetry breaking in NEXAFS spectra of protonated species we present a high resolution NEXAFS spectrum of protonated dinitrogen, the diazynium ion N2H+. By ab initio calculations we show that the spectrum consists of a superposition of two nitrogen 1s absorption spectra, each including a π∗ band, and a nitrogen 1s to H+ charge transfer band followed by a weak irregular progression of high energy excitations. Calculations also show that, as an effect of symmetry breaking by protonation, the π∗ transitions are separated by 0.23 eV, only slightly exceeding the difference in the corresponding dark (symmetry forbidden) and bright (symmetry allowed) core excitations of neutral N2. By DFT and calculations and vibrational analysis, the complex π∗ excitation band of N2H+ is understood as due to the superposition of the significantly different vibrational progressions of excitations from terminal and central nitrogen atoms, both leading to bent final state geometries. We also show computationally that the electronic structure of the charge transfer excitation smoothly depends on the nitrogen-proton distance and that there is a clear extension of the spectra going from infinity to close nitrogen-proton distance where fine structures show some, although not fully detailed, similarities. An interesting feature of partial localization of the nitrogen core orbitals, with a strong, non-monotonous, variation with nitrogen-proton distance could be highlighted. Specific effects could be unraveled when comparing molecular cation NEXAFS spectra, as represented by recently recorded spectra of N2+ and CO+, and spectra of protonated molecules as represented here by the N2H+ ion. Both types containing rich physical effects not represented in NEXAFS of neutral molecules because of the positive charge, whereas protonation also breaks the symmetry. The effect of the protonation on dinitrogen can be separated in charge, which extends the high-energy part of the spectrum, and symmetry-breaking, which is most clearly seen in the low-energy π∗ transition.
Ämnesord
- NATURVETENSKAP -- Kemi -- Fysikalisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Physical Chemistry (hsv//eng)
- NATURVETENSKAP -- Kemi -- Teoretisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)
- NATURVETENSKAP -- Fysik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences (hsv//eng)
Nyckelord
- Absorption spectroscopy
- Calculations
- Charge transfer
- Electronic structure
- Excited states
- Ions
- Molecules
- Nitrogen
- Ab initio calculations
- Charge transfer bands
- Charge-transfer excitations
- Partial localization
- Protonated molecules
- Protonated species
- Vibrational analysis
- Vibrational progressions
- Protonation
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
Hitta via bibliotek
Till lärosätets databas
- Av författaren/redakt...
-
Couto, Rafael Ca ...
-
Hua, W.
-
Lindblad, Rebeck ...
-
Kjellsson, Ludvi ...
-
Sorensen, Stacey ...
-
Kubin, M.
-
visa fler...
-
Bülow, C.
-
Timm, M.
-
Zamudio-Bayer, V ...
-
Von Issendorff, ...
-
Söderström, Joha ...
-
Lau, J. T.
-
Rubensson, Jan-E ...
-
Ågren, Hans
-
Carravetta, V.
-
visa färre...
- Om ämnet
-
- NATURVETENSKAP
-
NATURVETENSKAP
-
och Kemi
-
och Fysikalisk kemi
-
- NATURVETENSKAP
-
NATURVETENSKAP
-
och Kemi
-
och Teoretisk kemi
-
- NATURVETENSKAP
-
NATURVETENSKAP
-
och Fysik
- Artiklar i publikationen
-
Physical Chemist ...
- Av lärosätet
-
Kungliga Tekniska Högskolan
-
Uppsala universitet
-
Lunds universitet