Spectral shifts of the n → π* and π → π* transitions of uracil based on a modified form of solvent reorganization energy

Hai Sheng Ren, Yun Kui Li, Quan Zhu, Jun Zhu, Xiang Yuan Li

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

According to our recent studies on the nonequilibrium solvation, the solvent reorganization energy is found to be the cost of maintaining the residual polarization P′, which equilibrates with the extra electric field Eex. On the basis of this solvent reorganization energy and the well-established equilibrium solvation energy, a novel and reasonable expression for the spectral shift of the electronic absorption spectra is proposed in this work. Furthermore, the two lowest transitions of uracil in aqueous solution are investigated as test cases with the TDDFT/6-311++G** method. The obtained spectral shift is 0.48 eV for n → π* transition and -0.14 eV for π → π* transition, agreeing well with available experimental results. The contributions to the shift are discussed and the electrostatic plus polarization components are found to be crucial for the electronic absorption spectra of uracil in aqueous solution.

Original languageEnglish (US)
Pages (from-to)13284-13291
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number38
DOIs
StatePublished - Oct 14 2012

Fingerprint Dive into the research topics of 'Spectral shifts of the n → π* and π → π* transitions of uracil based on a modified form of solvent reorganization energy'. Together they form a unique fingerprint.

Cite this