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Infrared linear dichroism in stretched films: Quantum mechanical approach within the polarizable continuum model
Author(s) -
Cappelli Chiara,
Corni Stefano,
Mennucci Benedetta,
Tomasi Jacopo,
Cammi Roberto
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20523
Subject(s) - polarizability , infrared , linear dichroism , molecule , chemistry , transition dipole moment , polarizable continuum model , quantum , molecular physics , polarization (electrochemistry) , dichroism , formalism (music) , physics , quantum mechanics , circular dichroism , crystallography , musical , art , visual arts , solvation
In this work we discuss how environmental effects on vibrational transition moment directions for molecules dispersed in stretched films can be accounted for via the integral equation formalism polarizable continuum model (IEFPCM). In particular, effects related to the matrix polarization induced by the probing field (cavity field terms) are taken into account. Calculations are performed for three DNA‐related molecules (9‐methyladenine, 7‐methyladenine, and 2‐amino‐9‐methylpurine) for which infrared linear dichroism (IR LD) has been measured experimentally. By combining experimental data and calculations, different parameters of the film (Saupe order parameters and orientational axis direction) can be obtained and used to give “experimental” estimates of transition moment directions. The results show the importance of accounting for the environment surrounding the molecule in transition moment calculations. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005