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An interaction energy driven biased sampling technique: A faster route to ionization spectra in condensed phase
Author(s) -
Bose Samik,
Ghosh Debashree
Publication year - 2017
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24875
Subject(s) - phase space , ionization , chemistry , ionization energy , chromophore , sampling (signal processing) , ion , quantum , phase (matter) , aqueous solution , electron , spectral line , convergence (economics) , chemical physics , molecular physics , statistical physics , physics , quantum mechanics , photochemistry , optics , organic chemistry , detector , economics , economic growth
We introduce a computationally efficient approach for calculating spectroscopic properties, such as ionization energies (IEs) in the condensed phase. Discrete quantum mechanical/molecular mechanical (QM/MM) approaches for spectroscopic properties in a dynamic system, such as aqueous solution, need a large sample space to obtain converged estimates, especially for the cases where particle (electron) number is not conserved, such as IEs or electron affinities (EAs). We devise a biased sampling technique based on an approximate estimate of interaction energy between the solute and solvent, that accelerates the convergence and therefore, reduces the computational cost significantly. The approximate interaction energy also provides a good measure of the spectral width of the chromophores in the condensed phase. This technique has been tested and benchmarked for (i) phenol, (ii) HBDI anion (hydroxybenzylidene dimethyl imidazolinone), and (iii) thymine in water. © 2017 Wiley Periodicals, Inc.