Revealing the Electronic and Molecular Structure of Randomly Oriented Molecules by Polarized Two-Photon Spectroscopy
详细信息 查看全文
- 作者：Marcelo G. Vivas ; Daniel L. Silva ; Leonardo De Boni ; Yann Bretonniere ; Chantal Andraud ; Florence Laibe-Darbour ; J.-C. Mulatier ; Robert Zale艣ny ; Wojciech Bartkowiak ; Sylvio Canuto ; Cleber R. Mendonca
- 刊名：The Journal of Physical Chemistry Letters
- 出版年：2013
- 出版时间：May 16, 2013
- 年：2013
- 卷：4
- 期：10
- 页码：1753-1759
- 全文大小：435K
- 年卷期：v.4,no.10(May 16, 2013)
- ISSN：1948-7185
文摘
In this Letter, we explored the use of polarized two-photon absorption (2PA) spectroscopy, which brings additional information when compared to methods that do not use polarization control, to investigate the electronic and molecular structure of two chromophores (FD43 and FD48) based on phenylacetylene moieties. The results were analyzed using quantum chemical calculations of the two-photon transition strengths for circularly and linearly polarized light, provided by the response function formalism. On the basis of these data, it was possible to distinguish and identify the excited electronic states responsible for the lowest-energy 2PA-allowed band in both chromophores. By modeling the 2PA circular鈥搇inear dichroism, within the sum-over-essential states approach, we obtained the relative orientation between the dipole moments that are associated with the molecular structure of the chromophores in solution. This result allowed to correlate the V-shape structure of the FD48 chromophore and the quantum-interference-modulated 2PA strength.