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Monitoring Hydrogen/Deuterium Tautomerization in Transient Isomers of Single Porphine by Highly Localized Plasmonic Field
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Teoretisk kemi och biologi.
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Teoretisk kemi och biologi.ORCID-id: 0000-0002-3282-0711
Shandong Normal Univ, Shandong Prov Key Lab Med Phys & Image Proc Techn, Sch Phys & Elect, Jinan 250014, Shandong, Peoples R China..
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Teoretisk kemi och biologi.ORCID-id: 0000-0003-0007-0394
2019 (Engelska)Ingår i: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 123, nr 17, s. 11081-11093Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Inner proton transfer between two trans isomers (tautomerization) in porphyrins plays a crucial role in many biological systems as well as molecular nanotechnology. Although the stepwise mechanism of tautomerization is well accepted, the involved intermediate cis-isomer has not been directly detected owing to its short lifetime and the extremely low intensities of corresponding hydrogen vibrations. Here, taking a single porphine as the prototype, we theoretically demonstrate that Raman intensities of the hydrogen vibrations become accessible under the highly localized plasmonic field because of the symmetry breaking effect. In addition, with the ultrafast incident excitations, we find that Raman signals of cis-porphine could be distinguished from the stable trans isomer, suggesting a general protocol for the direct characterization of transient isomers. Moreover, calculated results reveal that the position of inner hydrogen/deuterium can be unambiguously visualized from Raman images of the corresponding stretching modes, providing a unique optical means for the chemical monitoring of tautomerization in porphine and its derivatives.

Ort, förlag, år, upplaga, sidor
AMER CHEMICAL SOC , 2019. Vol. 123, nr 17, s. 11081-11093
Nationell ämneskategori
Fysikalisk kemi
Identifikatorer
URN: urn:nbn:se:kth:diva-252384DOI: 10.1021/acs.jpcc.9b00398ISI: 000466988600040Scopus ID: 2-s2.0-85065302261OAI: oai:DiVA.org:kth-252384DiVA, id: diva2:1326608
Anmärkning

QC 20190618

Tillgänglig från: 2019-06-18 Skapad: 2019-06-18 Senast uppdaterad: 2019-11-07Bibliografiskt granskad
Ingår i avhandling
1. High Resolution Tip-Enhanced Raman Images of Single Molecules from First Principles Simulations
Öppna denna publikation i ny flik eller fönster >>High Resolution Tip-Enhanced Raman Images of Single Molecules from First Principles Simulations
2019 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

With the precise control of spatially confined plasmon (SCP), tip-enhanced Raman spectroscopy (TERS) has achieved sub-nanometer resolution, leading to the chemical and physical characterization of the single molecule by optical Raman images. In the high resolution TERS measurements, the SCP spatial distribution generates the position-dependent Raman images. The position dependence challenges the conventional response theory, because the assumption of interactions between the molecule and the uniform electromagnetic field does not hold anymore. Moreover, as an emerging technology, potential applications of high resolution TERS are required to be fully explored. In this thesis, the developed theory for modeling high resolution Raman images is presented. By taking a series of typical molecular systems as examples, we theoretically predict some fine applications of single-molecule TERS.

The first part of the thesis introduces the development of Raman spectroscopy and images. To achieve the final target of single molecule characterization, high spatial resolution single-molecule TERS is established and improved. As a nondestructive measuring tool, Raman imaging technology offers the means to study single molecules with unprecedented spatial resolution.

The high resolution Raman images theory with detailed derivations is given in the second part of the thesis. The key factor is to take the inhomogeneous spatial distribution of SCP field into account, when we construct the interaction Hamiltonian between the localized light field and the molecule. This makes the numerical simulations of Raman images feasible.

Other parts of the thesis give some theoretical predictions for potential applications of the emerging Raman imaging technology. Specifically, resonance Raman images can visualize the geometric changes of a single molecule switch and the intramolecular structure in real space. Since the localized plasmonic field can affect the electron transition, the excited quantum states can thus be effectively manipulated. This breaks down the intrinsic spatial selection rule imposed in conventional spectra. In addition, an effective linear response algorithm is used to simulate nonresonance Raman images. The unique superiority of spatial vibration resolution from non-resonance cases provides rich information about the single molecule. By constructing images from different vibrational modes, the spatial chemical distribution within a single molecule can be visualized. All these findings will facilitate fine applications of the emerging TERS technology in the coming years.

Ort, förlag, år, upplaga, sidor
Kungliga Tekniska högskolan, 2019. s. 69
Serie
TRITA-CBH-FOU ; 67
Nyckelord
First Principles, Tip-Enhanced Raman Images, light-matter interactions at the nanoscale
Nationell ämneskategori
Naturvetenskap
Forskningsämne
Teoretisk kemi och biologi
Identifikatorer
urn:nbn:se:kth:diva-263652 (URN)978-91-7873-373-6 (ISBN)
Disputation
2019-12-06, FP 41, Roslagstullsbacken 33, Stockholm, 14:00 (Engelska)
Opponent
Handledare
Anmärkning

QC 2019-11-14

Tillgänglig från: 2019-11-14 Skapad: 2019-11-07 Senast uppdaterad: 2019-11-14Bibliografiskt granskad

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Xie, ZhenDuan, SaiLuo, Yi

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