Which charge definition for describing the crystal polarizing field and the and of organic crystals?

2015
journal article
article
20
dc.abstract.enThe impact of atomic charge definition for describing the crystal polarizing electric field has been assessed in view of predicting the linear and nonlinear optical susceptibilities of molecular crystals. In this approach, the chromophores are embedded in the electric field of its own point charges, which are evaluated through a self-consistent procedure including charge scaling to account for the screening of the dielectric. Once the crystal field is determined, dressed molecular polarizabilities and hyperpolarizabilities are calculated and used as input of an electrostatic interaction scheme to evaluate the crystal linear and nonlinear optical responses. It is observed that many charge definitions (i) based on partitioning the electron density (QTAIM), (ii) obtained by analyzing the quantum-chemical wavefunction (Mulliken, MBS, and NBO), and (iii) derived by fitting to the electrostatic potential (MK, CHelpG, and HLYGAt) give very consistent results and are equally valid whereas Hirshfeld partitioning and CM5 charge parametrizations underestimate the refractive indices and second-order nonlinear optical susceptibilities. An alternative approach omitting charge scaling is demonstrated to overestimate the different crystal optical properties. On the other hand, the molecule embedding approach provides results in close agreement with those calculated with a charge field obtained from periodic boundary condition calculations.pl
dc.affiliationWydział Chemii : Zakład Krystalochemii i Krystalofizykipl
dc.contributor.authorSeidler, Tomasz - 106182 pl
dc.contributor.authorChampagne, Benoîtpl
dc.date.accessioned2015-12-02T11:08:53Z
dc.date.available2015-12-02T11:08:53Z
dc.date.issued2015pl
dc.description.number29pl
dc.description.physical19546-19556pl
dc.description.volume17pl
dc.identifier.doi10.1039/C5CP03248Bpl
dc.identifier.eissn1463-9084pl
dc.identifier.issn1463-9076pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/17404
dc.languageengpl
dc.language.containerengpl
dc.rights.licencebez licencji
dc.subtypeArticlepl
dc.titleWhich charge definition for describing the crystal polarizing field and the $\chi^{(1)}$ and $\chi^{(2)}$ of organic crystals?pl
dc.title.journalPhysical Chemistry Chemical Physicspl
dc.typeJournalArticlepl
dspace.entity.typePublication
dc.abstract.enpl
The impact of atomic charge definition for describing the crystal polarizing electric field has been assessed in view of predicting the linear and nonlinear optical susceptibilities of molecular crystals. In this approach, the chromophores are embedded in the electric field of its own point charges, which are evaluated through a self-consistent procedure including charge scaling to account for the screening of the dielectric. Once the crystal field is determined, dressed molecular polarizabilities and hyperpolarizabilities are calculated and used as input of an electrostatic interaction scheme to evaluate the crystal linear and nonlinear optical responses. It is observed that many charge definitions (i) based on partitioning the electron density (QTAIM), (ii) obtained by analyzing the quantum-chemical wavefunction (Mulliken, MBS, and NBO), and (iii) derived by fitting to the electrostatic potential (MK, CHelpG, and HLYGAt) give very consistent results and are equally valid whereas Hirshfeld partitioning and CM5 charge parametrizations underestimate the refractive indices and second-order nonlinear optical susceptibilities. An alternative approach omitting charge scaling is demonstrated to overestimate the different crystal optical properties. On the other hand, the molecule embedding approach provides results in close agreement with those calculated with a charge field obtained from periodic boundary condition calculations.
dc.affiliationpl
Wydział Chemii : Zakład Krystalochemii i Krystalofizyki
dc.contributor.authorpl
Seidler, Tomasz - 106182
dc.contributor.authorpl
Champagne, Benoît
dc.date.accessioned
2015-12-02T11:08:53Z
dc.date.available
2015-12-02T11:08:53Z
dc.date.issuedpl
2015
dc.description.numberpl
29
dc.description.physicalpl
19546-19556
dc.description.volumepl
17
dc.identifier.doipl
10.1039/C5CP03248B
dc.identifier.eissnpl
1463-9084
dc.identifier.issnpl
1463-9076
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/17404
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights.licence
bez licencji
dc.subtypepl
Article
dc.titlepl
Which charge definition for describing the crystal polarizing field and the $\chi^{(1)}$ and $\chi^{(2)}$ of organic crystals?
dc.title.journalpl
Physical Chemistry Chemical Physics
dc.typepl
JournalArticle
dspace.entity.type
Publication
Affiliations

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