Is ammonia a better solvent than water for contact ion Pairs?
The existence of a charge-transfer-to-solvent process when a KI contact ion pair (GP) dissolved in supercritical water (SCW) is excited by UV light was confirmed by use of electronic structure calculations applied to molecular dynamics trajectories. We observed similar behavior with fluid density as...
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todo:paper_15206106_v112_n38_p11990_Sciaini2023-10-03T16:20:14Z Is ammonia a better solvent than water for contact ion Pairs? Sciaini, G. Marceca, E. Fernández-Prini, R. Ammonia Dissolution Dynamics Electric excitation Electronic structure Ions Molecular dynamics Quantum chemistry Charge-transfer-to-solvent Contact ion pairs Destabilizing effects Distinct features Electronic-structure calculations Excited-states Fluid densities Ion pairs Molecular dynamics trajectories Solvation shells Solvent effects Solvent molecules Solvent-solvent interactions Supercritical ammonia Supercritical solvents Supercritical water U V light Solvents The existence of a charge-transfer-to-solvent process when a KI contact ion pair (GP) dissolved in supercritical water (SCW) is excited by UV light was confirmed by use of electronic structure calculations applied to molecular dynamics trajectories. We observed similar behavior with fluid density as that found for the KI-CIP in supercritical ammonia (SCA); nevertheless, there are some distinct features in the two supercritical solvents. First, the effect of the solvent field due to the molecules lying beyond the first solvation shell is very different in SCW compared with that observed in SCA; in SCW it actually has a destabilizing effect over the ground and excited states. Second, our results for the thermodynamic behavior of the CIP indicate that SCA is better solvent than SCW for this species. The differences found can be attributed to the solvent molecules surrounding the CIP and bridging the two ions; they shield more efficiently the ion pair from long-range solvent effects in SCA. The different behavior is partially attributed to a stronger solvent-solvent interaction in SCW than in SCA. © 2008 American Chemical Society. Fil:Sciaini, G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Marceca, E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Fernández-Prini, R. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_15206106_v112_n38_p11990_Sciaini |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Ammonia Dissolution Dynamics Electric excitation Electronic structure Ions Molecular dynamics Quantum chemistry Charge-transfer-to-solvent Contact ion pairs Destabilizing effects Distinct features Electronic-structure calculations Excited-states Fluid densities Ion pairs Molecular dynamics trajectories Solvation shells Solvent effects Solvent molecules Solvent-solvent interactions Supercritical ammonia Supercritical solvents Supercritical water U V light Solvents |
| spellingShingle |
Ammonia Dissolution Dynamics Electric excitation Electronic structure Ions Molecular dynamics Quantum chemistry Charge-transfer-to-solvent Contact ion pairs Destabilizing effects Distinct features Electronic-structure calculations Excited-states Fluid densities Ion pairs Molecular dynamics trajectories Solvation shells Solvent effects Solvent molecules Solvent-solvent interactions Supercritical ammonia Supercritical solvents Supercritical water U V light Solvents Sciaini, G. Marceca, E. Fernández-Prini, R. Is ammonia a better solvent than water for contact ion Pairs? |
| topic_facet |
Ammonia Dissolution Dynamics Electric excitation Electronic structure Ions Molecular dynamics Quantum chemistry Charge-transfer-to-solvent Contact ion pairs Destabilizing effects Distinct features Electronic-structure calculations Excited-states Fluid densities Ion pairs Molecular dynamics trajectories Solvation shells Solvent effects Solvent molecules Solvent-solvent interactions Supercritical ammonia Supercritical solvents Supercritical water U V light Solvents |
| description |
The existence of a charge-transfer-to-solvent process when a KI contact ion pair (GP) dissolved in supercritical water (SCW) is excited by UV light was confirmed by use of electronic structure calculations applied to molecular dynamics trajectories. We observed similar behavior with fluid density as that found for the KI-CIP in supercritical ammonia (SCA); nevertheless, there are some distinct features in the two supercritical solvents. First, the effect of the solvent field due to the molecules lying beyond the first solvation shell is very different in SCW compared with that observed in SCA; in SCW it actually has a destabilizing effect over the ground and excited states. Second, our results for the thermodynamic behavior of the CIP indicate that SCA is better solvent than SCW for this species. The differences found can be attributed to the solvent molecules surrounding the CIP and bridging the two ions; they shield more efficiently the ion pair from long-range solvent effects in SCA. The different behavior is partially attributed to a stronger solvent-solvent interaction in SCW than in SCA. © 2008 American Chemical Society. |
| format |
JOUR |
| author |
Sciaini, G. Marceca, E. Fernández-Prini, R. |
| author_facet |
Sciaini, G. Marceca, E. Fernández-Prini, R. |
| author_sort |
Sciaini, G. |
| title |
Is ammonia a better solvent than water for contact ion Pairs? |
| title_short |
Is ammonia a better solvent than water for contact ion Pairs? |
| title_full |
Is ammonia a better solvent than water for contact ion Pairs? |
| title_fullStr |
Is ammonia a better solvent than water for contact ion Pairs? |
| title_full_unstemmed |
Is ammonia a better solvent than water for contact ion Pairs? |
| title_sort |
is ammonia a better solvent than water for contact ion pairs? |
| url |
http://hdl.handle.net/20.500.12110/paper_15206106_v112_n38_p11990_Sciaini |
| work_keys_str_mv |
AT sciainig isammoniaabettersolventthanwaterforcontactionpairs AT marcecae isammoniaabettersolventthanwaterforcontactionpairs AT fernandezprinir isammoniaabettersolventthanwaterforcontactionpairs |
| _version_ |
1782025987075080192 |