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Solvatochromism in a Pyridinium Cyclopentadienylide: Insights from a Sequential Car-Parrinello QM/MM and TD-DFT/Semicontinuum Approach
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-0185-5724
2014 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 118, no 26, 7358-7366 p.Article in journal (Refereed) Published
Abstract [en]

Understanding the working mechanism and establishing structure-property relationships for optical probes is an essential step to develop design principles for novel molecular probes. Here we study optical properties of a small-sized dielectric probe, namely, 4-carbamido pyridinium cydopentadienylide (CPYC) in benzene and in water solvents using a sequential approach. In particular, the structure modeling has been carried out using a Car-Parrinello hybrid QM/MM molecular dynamics approach, while the excitation energies were computed using time dependent density functional theory. To incorporate the solvent effect either a polarizable continuum model or a semicontinuum description was employed. The molecular dipole moment of CPYC in water is more than two times larger than in benzene solvent. The positive and negative charges tend to accumulate on pyridinium and cyclopentadienylide rings, respectively, with increasing solvent polarity. Significant solvent-induced geometrical changes have been reported in CPYC and this contributes to a significant red shift in spectra. Even though the absorption maxima for CPYC in benzene and water solvents were underestimated, the solvatochromic shift has been reproduced in good agreement with experiments. We also report that CPYC can be used as a two photon probe.

Place, publisher, year, edition, pages
2014. Vol. 118, no 26, 7358-7366 p.
Keyword [en]
Benzene, Continuum mechanics, Molecular dynamics, Probes, Water absorption, Geometrical changes, Molecular dipole moment, Polarizable continuum model, Sequential approach, Solvatochromic shifts, Structure modeling, Structure property relationships, Time dependent density functional theory
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-148612DOI: 10.1021/jp410854bISI: 000338693000015ScopusID: 2-s2.0-84903795023OAI: diva2:737231

QC 20140812

Available from: 2014-08-12 Created: 2014-08-11 Last updated: 2014-08-12Bibliographically approved

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Murugan, N. Arul
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