Adsorbate-induced absorption redshift in an organic-inorganic cluster conjugate: Electronic effects of surfactants and organic adsorbates on the lowest excited states of a methanethiol-CdSe conjugate

Christopher Liu, Sang Yoon Chung, Sungyul Lee, Shimon Weiss, Daniel Neuhauser

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25 Scopus citations

Abstract

Bioconjugated CdSe quantum dots are promising reagents for bioimaging applications. Experimentally, the binding of a short peptide has been found to redshift the optical absorption of nanoclusters [J. Tsay, J. Phys. Chem. B 109, 1669 (2005)]. This study examines this issue by performing density functional theory (DFT) and time-dependent-DFT calculations to study the ground state and low-lying excited states of (CdSe)6 [SCH3]-, a transition metal complex built by binding methanethiolate to a CdSe molecular cluster. Natural bond orbital results show that the redshift is caused by ligand-inorganic cluster orbital interaction. The highest occupied molecular orbital (HOMO) of (CdSe)6 is dominated by selenium 4p orbitals; in contrast, the HOMO of (CdSe)6 [SCH3]- is dominated by sulfur 3p orbitals. This difference shows that [SCH 3]- binding effectively introduces filled sulfur orbitals above the selenium 4p orbitals of (CdSe)6. The resulting smaller HOMO-LUMO gap of (CdSe) 6 [SCH3]- indeed leads to redshifts in its excitation energies compared to (CdSe) 6. In contrast, binding of multiple NH3 destabilizes cadmium 5p orbitals, which contribute significantly to the lowest unoccupied molecular orbital (LUMO) of (CdSe)6, while leaving the selenium 4p orbitals near the HOMO relatively unaffected. This has the effect of widening the HOMO-LUMO gap of (CdSe) 6 6NH3 compared to (CdSe) 6. As expected, the excitation energies of the passivated (CdSe) 6 6NH3 are also blueshifted compared to (CdSe)6. As far as NH3 is a faithful representation of a surfactant, the results clearly illustrate the differences between the electronic effects of an alkylthiolate versus those of surfactant molecules. Surface passivation of (CdSe) 6 [SCH 3]- is then simulated by coating it with multiple NH 3 molecules. The results suggest that the [SCH3] - adsorption induces a redshift in the excitation energies in a surfactant environment.

Original languageEnglish
Article number174705
JournalJournal of Chemical Physics
Volume131
Issue number17
DOIs
StatePublished - 7 Nov 2009
Externally publishedYes

Bibliographical note

Funding Information:
This work was supported by NSF, Grant No. DMS0835863 (D.N.), NIH Grant No. R01-EB000312 (S.W.). S.L. thanks the financial support by GRRC. C.L. thanks the support of an UCLA Dissertation Year Fellowship.

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