Origin of the Red Shift for the Lowest Singlet π → π Charge-Transfer Absorption of p‑Nitroaniline in Supercritical CO2
The origin of the unusual solvatochromic shift of p-nitroaniline (PNA) in supercritical carbon dioxide (SCCO2) is theoretically investigated on the basis of experimental data. Ab initio quantum chemistry calculations have been employed to unveil the interaction of CO2 with this archetypical molecule...
Saved in:
Published in | Journal of chemical theory and computation Vol. 10; no. 4; pp. 1554 - 1562 |
---|---|
Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
08.04.2014
|
Online Access | Get full text |
Cover
Loading…
Abstract | The origin of the unusual solvatochromic shift of p-nitroaniline (PNA) in supercritical carbon dioxide (SCCO2) is theoretically investigated on the basis of experimental data. Ab initio quantum chemistry calculations have been employed to unveil the interaction of CO2 with this archetypical molecule. It is demonstrated that the nitro group of PNA works as an electron-donating site binding to the electron-deficient carbon atom of CO2, most probably via a Lewis acid–base interaction. Moreover, a cooperative C–H···O hydrogen bond seems to act as an additional stabilizing source during the solvation process of PNA in SCCO2. To support the influence of solute–solvent specific interactions on the lowest singlet π → π* charge-transfer excitation, we perform a sequential Monte Carlo time-dependent density functional theory simulation to evaluate the excited states of PNA in SCCO2 (T = 315 K, ρ = 0.81 g/cm3). A critical assessment of this simulation, compared to calculations carried out within the polarized continuum model, gives strong evidence that our proposed complexes are important in describing the solvatochromic shift of PNA in SCCO2. The calculated red shift from the gas phase accounts for 66% to 80% (depending on the degree of complexation) of the experimental data. Finally, these results also alleviate possible failures commonly attributed to long-range corrected functionals in reproducing the solvatochromism of PNA. |
---|---|
AbstractList | The origin of the unusual solvatochromic shift of p-nitroaniline (PNA) in supercritical carbon dioxide (SCCO2) is theoretically investigated on the basis of experimental data. Ab initio quantum chemistry calculations have been employed to unveil the interaction of CO2 with this archetypical molecule. It is demonstrated that the nitro group of PNA works as an electron-donating site binding to the electron-deficient carbon atom of CO2, most probably via a Lewis acid-base interaction. Moreover, a cooperative C-H···O hydrogen bond seems to act as an additional stabilizing source during the solvation process of PNA in SCCO2. To support the influence of solute-solvent specific interactions on the lowest singlet π → π* charge-transfer excitation, we perform a sequential Monte Carlo time-dependent density functional theory simulation to evaluate the excited states of PNA in SCCO2 (T = 315 K, ρ = 0.81 g/cm(3)). A critical assessment of this simulation, compared to calculations carried out within the polarized continuum model, gives strong evidence that our proposed complexes are important in describing the solvatochromic shift of PNA in SCCO2. The calculated red shift from the gas phase accounts for 66% to 80% (depending on the degree of complexation) of the experimental data. Finally, these results also alleviate possible failures commonly attributed to long-range corrected functionals in reproducing the solvatochromism of PNA. The origin of the unusual solvatochromic shift of p-nitroaniline (PNA) in supercritical carbon dioxide (SCCO2) is theoretically investigated on the basis of experimental data. Ab initio quantum chemistry calculations have been employed to unveil the interaction of CO2 with this archetypical molecule. It is demonstrated that the nitro group of PNA works as an electron-donating site binding to the electron-deficient carbon atom of CO2, most probably via a Lewis acid–base interaction. Moreover, a cooperative C–H···O hydrogen bond seems to act as an additional stabilizing source during the solvation process of PNA in SCCO2. To support the influence of solute–solvent specific interactions on the lowest singlet π → π* charge-transfer excitation, we perform a sequential Monte Carlo time-dependent density functional theory simulation to evaluate the excited states of PNA in SCCO2 (T = 315 K, ρ = 0.81 g/cm3). A critical assessment of this simulation, compared to calculations carried out within the polarized continuum model, gives strong evidence that our proposed complexes are important in describing the solvatochromic shift of PNA in SCCO2. The calculated red shift from the gas phase accounts for 66% to 80% (depending on the degree of complexation) of the experimental data. Finally, these results also alleviate possible failures commonly attributed to long-range corrected functionals in reproducing the solvatochromism of PNA. |
Author | Rivelino, Roberto Canuto, Sylvio Hidalgo, Marcelo |
AuthorAffiliation | Instituto de Física Universidade de São Paulo Universidade Federal da Bahia |
AuthorAffiliation_xml | – name: Universidade de São Paulo – name: Universidade Federal da Bahia – name: Instituto de Física |
Author_xml | – sequence: 1 givenname: Marcelo surname: Hidalgo fullname: Hidalgo, Marcelo – sequence: 2 givenname: Roberto surname: Rivelino fullname: Rivelino, Roberto email: rivelino@ufba.br – sequence: 3 givenname: Sylvio surname: Canuto fullname: Canuto, Sylvio email: canuto@if.us.br |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/26580369$$D View this record in MEDLINE/PubMed |
BookMark | eNo9kc9KAzEQxoMoaqsHX0ByEbxUN3823T1K8R8UC1bPSzadtJFtsiZZRPDQk3d9Md-hT-K21p5mGH58M998HbRrnQWETkhyQRJKLlXkCUkyAjvokKQ87-WCit1tT7ID1AnhJUkY45TtowMq0ixhIj9EHyNvpsZip3GcAX6ECR7PjI5YO7-eDN0bhIjHxk4riPhngZef36symEk_hd6TlzZo8PiqDM7X0bi1WL1cfD2Y6J20pjIWcLtj3NTglTfRKFnhwYgeoT0tqwDHm9pFzzfXT4O73nB0ez-4GvYk5SSuHCit-pqyiSL5hGe0TLWguRSCCVBlmvFUsVRCWnKdlxIyyvtCCQFcl0QA66LzP93au9emtVPMTVBQVdKCa0JB-ixlNOM5a9HTDdqUc5gUtTdz6d-L_4-1wNkfIFUoXlzjbXt5QZJilUSxTYL9AmBYfSU |
ContentType | Journal Article |
Copyright | Copyright © 2014 American Chemical Society |
Copyright_xml | – notice: Copyright © 2014 American Chemical Society |
DBID | NPM 7X8 |
DOI | 10.1021/ct401081e |
DatabaseName | PubMed MEDLINE - Academic |
DatabaseTitle | PubMed MEDLINE - Academic |
DatabaseTitleList | MEDLINE - Academic PubMed |
Database_xml | – sequence: 1 dbid: NPM name: PubMed url: https://proxy.k.utb.cz/login?url=http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed sourceTypes: Index Database |
DeliveryMethod | fulltext_linktorsrc |
Discipline | Chemistry |
EISSN | 1549-9626 |
EndPage | 1562 |
ExternalDocumentID | 26580369 h97711467 |
Genre | Journal Article |
GroupedDBID | 4.4 53G 55A 5GY 7~N AABXI ABMVS ABUCX ACGFS ACIWK ACS AEESW AENEX AFEFF ALMA_UNASSIGNED_HOLDINGS AQSVZ CS3 D0L DU5 EBS ED ED~ EJD F5P GNL IH9 J9A JG JG~ LG6 P2P RNS ROL UI2 VF5 VG9 W1F 5VS ABJNI ABQRX ADHLV AHGAQ BAANH CUPRZ GGK NPM 7X8 |
ID | FETCH-LOGICAL-a241t-961cfc7f23dc19d482b5f629a6636ecb5845c35ae5b4f9bae82476c66e4fb16e3 |
IEDL.DBID | ACS |
ISSN | 1549-9618 |
IngestDate | Fri Aug 16 07:35:42 EDT 2024 Sat Sep 28 08:02:40 EDT 2024 Thu Aug 27 13:43:13 EDT 2020 |
IsPeerReviewed | true |
IsScholarly | true |
Issue | 4 |
Language | English |
LinkModel | DirectLink |
MergedId | FETCHMERGED-LOGICAL-a241t-961cfc7f23dc19d482b5f629a6636ecb5845c35ae5b4f9bae82476c66e4fb16e3 |
Notes | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
PMID | 26580369 |
PQID | 1735328493 |
PQPubID | 23479 |
PageCount | 9 |
ParticipantIDs | proquest_miscellaneous_1735328493 pubmed_primary_26580369 acs_journals_10_1021_ct401081e |
ProviderPackageCode | JG~ 55A AABXI GNL VF5 7~N VG9 W1F ACS AEESW AFEFF ABMVS ABUCX IH9 AQSVZ ED~ UI2 |
PublicationCentury | 2000 |
PublicationDate | 2014-04-08 |
PublicationDateYYYYMMDD | 2014-04-08 |
PublicationDate_xml | – month: 04 year: 2014 text: 2014-04-08 day: 08 |
PublicationDecade | 2010 |
PublicationPlace | United States |
PublicationPlace_xml | – name: United States |
PublicationTitle | Journal of chemical theory and computation |
PublicationTitleAlternate | J. Chem. Theory Comput |
PublicationYear | 2014 |
Publisher | American Chemical Society |
Publisher_xml | – name: American Chemical Society |
SSID | ssj0033423 |
Score | 2.2653453 |
Snippet | The origin of the unusual solvatochromic shift of p-nitroaniline (PNA) in supercritical carbon dioxide (SCCO2) is theoretically investigated on the basis of... |
SourceID | proquest pubmed acs |
SourceType | Aggregation Database Index Database Publisher |
StartPage | 1554 |
Title | Origin of the Red Shift for the Lowest Singlet π → π Charge-Transfer Absorption of p‑Nitroaniline in Supercritical CO2 |
URI | http://dx.doi.org/10.1021/ct401081e https://www.ncbi.nlm.nih.gov/pubmed/26580369 https://search.proquest.com/docview/1735328493 |
Volume | 10 |
hasFullText | 1 |
inHoldings | 1 |
isFullTextHit | |
isPrint | |
link | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwhZ1Nb9QwEIZHpRzgAuWrLB-VEVxTGjtO4mO1tKoQtBJLpd4i25mBVaVklc1eqh564g5_jP_QX8LY2SAkVDhFihIn8iR-n2TsdwDepEhksMYkVXVYkqNdYqSuE8oI0Sr-KIr_dD8e50en2fszfbYBr2_I4Mv0re_5E4CFC2_BbRlmDgb-mc7G4VYFC7toipoFq8m0HO2D_jw1SI9f3gyRUUwO78O7cUnOMIfkfHfVu11_8bdD47_ucwvurWFS7A_RfwAb2DyEO9OxhtsjuDyJda9ES4JBT3zCWsy-zqkXjKpxz4c2WCWIGQsYB1D8vBLX336ETUjDf8EkShlhJ_bdsu3i8BIaW1xffT-e911rm3ngVMHXmK0W2Pl15QQxPZGP4fTw4PP0KFnXW0gs63gfes-TL0iq2qemzkrpNOXSWKaSHL1jVtFeaYvaZWScxVJmRe7zHDNyaY7qCWw2bYNPQUjjjLSayDJeWifLWpNKNWWIRbG3RxPY4YBU6_dlWcVUuEyr3504gVdjrCrus5DFsA22Kz60UFqxqBo1ge0hiNVicOaoJPMUS7J59r_mn8NdJp9hCk75Ajb7boUvmS56txOfrl-3FsxX |
link.rule.ids | 315,786,790,27109,27957,27958,57093,57143 |
linkProvider | American Chemical Society |
linkToHtml | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwjV1Nb9QwELWgHMqlfBW6fBRX4prS2HESH6sV1QLbrdRtpd4i25mBFVKySrKXqoeeuMMf4z_0lzB2soAqIThFipKJNeP4PXvsN4y9iQFRQwlRLEt_JEfZSAtVRpgggJE0KQprusezdHKefLhQF4NMjj8LQ41oyVIbkvi_1QXit66jmQDhF9xl91RG83BPg8bz9agrvZJd0EZNvOJknK9VhP581SOQa__OJQOmHD3oixOF1oStJF_2V53dd5e3hBr_r7kP2dZALflh3xcesTtQPWab43VFtyfs6iRUweI1cqJ9_BRKPv-8wI4TcQ13prUXTuBzgjMKJ_9xzW--fvcXn5T_BFEANoSGH9q2bsJg440tb66_zRZdU5tq4Vkrp2_MV0to3FBHgY9PxDY7P3p3Np5EQ_WFyBCqd96JDl2GQpYu1mWSC6swFdoQR0nBWWIuykllQNkEtTWQiyRLXZpCgjZOQT5lG1VdwQ7jQlstjEI0RDaNFXmpUMYKE4AsOzjAEdslHxbD39MWITEu4uKXE0dsbx2ygnzmcxqmgnpFj2ZSSYJYLUfsWR_LYtnrdBSC2BUBtH7-L_Ov2ebk7HhaTN_PPr5g94kT9Ztz8pdso2tW8Ip4R2d3Q4f7CfkX1MI |
linkToPdf | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwjV1Nb9QwELVKKwGXUr4XaDES15TGjpP4WC2sCpRdxFKpt8h2ZuiqUrJKshfUQ0-9lz_W_9Bf0rE3WyEkBKdIUTKxZmy_54z9hrG3MSBqKCGKZemP5CgbaaHKCBMEMJIWReGf7pdxenCUfDpWx_1C0Z-FoUa0ZKkNSXw_qucl9goD8TvX0WqAMAzusA3lC3d7KjScrmZe6dXsgj5q4lUn43ylJPT7qx6FXPt3PhlwZfSATW5bFLaTnO4uOrvrfv4h1vj_Td5imz3F5PvLPvGQrUH1iN0briq7PWZnk1ANi9fIif7xb1Dy6ckMO04ENtw5rL2AAp8SrFFY-dU5v7745S8-Of8DogBwCA3ft23dhEnHG5tfn1-OZ11Tm2rm2Sunb0wXc2hcX0-BDyfiCTsaffg-PIj6KgyRIXTvvCMdugyFLF2syyQXVmEqtCGukoKzxGCUk8qAsglqayAXSZa6NIUEbZyCfMrWq7qC54wLbbUwCtEQ6TRW5KVCGStMALJsbw8HbIf8WPSjqC1CglzExa0TB-zNKmwF-cznNkwF9YIezaSSBLVaDtizZTyL-VKvoxDEsgio9Yt_mX_N7n59PyoOP44_v2T3iRot9-jkr9h61yxgm-hHZ3dCn7sB2AvXPA |
openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Origin+of+the+Red+Shift+for+the+Lowest+Singlet+%CF%80+%E2%86%92+%CF%80+Charge-Transfer+Absorption+of+p%E2%80%91Nitroaniline+in+Supercritical+CO2&rft.jtitle=Journal+of+chemical+theory+and+computation&rft.au=Hidalgo%2C+Marcelo&rft.au=Rivelino%2C+Roberto&rft.au=Canuto%2C+Sylvio&rft.date=2014-04-08&rft.pub=American+Chemical+Society&rft.issn=1549-9618&rft.eissn=1549-9626&rft.volume=10&rft.issue=4&rft.spage=1554&rft.epage=1562&rft_id=info:doi/10.1021%2Fct401081e&rft.externalDocID=h97711467 |
thumbnail_l | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=1549-9618&client=summon |
thumbnail_m | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=1549-9618&client=summon |
thumbnail_s | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=1549-9618&client=summon |