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New Developments of a Multifrequency Virtual Spectrometer: Stereo‐Electronic, Dynamical, and Environmental Effects on Chiroptical Spectra
Author(s) -
Barone Vincenzo,
Baiardi Alberto,
Bloino Julien
Publication year - 2014
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22325
Subject(s) - anharmonicity , chemistry , vibronic spectroscopy , spectrometer , electronic structure , fortran , spectroscopy , software , theoretical physics , computational chemistry , statistical physics , quantum mechanics , physics , computer science , molecule , programming language , operating system , organic chemistry
Computational spectroscopy has recently evolved from a field reserved for specialists toward a general tool allowing interpretations and analyses of experimental results. However, the current practice of providing tables of transitions for rigid geometries, possibly tuned by phenomenological broadening, is by far too naive. In order to improve this situation in the last few years we have been developing a general, robust, and user‐friendly virtual spectrometer (VS) able to complement experimental studies for complex systems in condensed phases. The VS is based on flexible graphical pre‐ and postprocessing tools interfaced with general number‐crunching software. This last tool is rooted in several electronic structure methodologies (DFT, TD‐DFT, post‐Hartree‐Fock), powerful discrete/continuum models for describing environmental effects, and general vibrational and vibronic models. These last topics are the main focus of this work, which sketches our latest developments related to effective inclusion of anharmonic contributions, together with time‐independent and/or time‐dependent descriptions of vibronic transitions including Franck‐Condon, Herzberg‐Teller, and Duschinsky effects. Some test cases are described in some detail with the aim of showing the role of different effects in ruling vibrational (VCD) and electronic (ECD, CPL) chiral spectroscopies. Chirality 26:588–600, 2014 . © 2014 Wiley Periodicals, Inc.