| Attributs | Valeurs |
|---|
| type
| |
| Is Part Of
| |
| Subject
| |
| Title
| - Solvent Effects on the Photodissociation of Formic Acid: A Theoretical Study
|
| has manifestation of work
| |
| related by
| |
| Author
| |
| Abstract
| - Photodissociation of aqueous formic acid has been investigated with the CASSCF, DFT, and MR-CI methods.Solvent effects are considered as a combination of the hydrogen-bonding interaction from explicit H2Omolecules and the effects from the bulk surrounding H2O molecules using the polarizable continuum model.It is found that the hydrogen-bonding effect from the explicit water in the complex is the major factor toinfluence properties of aqueous formic acid, while the bulk surrounding H2O molecules has a noticeableinfluence on the structures of the complex. The direct C−O bond fission along the S1 pathway is predictedto be an important channel upon photolysis of aqueous formic acid at 200 nm, which is consistent withexperimental observation that aqueous formic acid dissociates predominantly into fragments of HCO andOH. The existence of a dark channel upon photolysis of aqueous formic acid at 200 nm is assigned as fastrelaxation from the S1 Franck−Condon geometry to the T1/S1 intersection and subsequent S1 → T1 intersystemcrossing process. S1 → S0 internal conversion followed by molecular elimination to CO + H2O is the mostprobable primary process for formation of carbon monoxide, which was observed with considerable yieldupon photolysis of aqueous formic acid at 253.7 nm.
|
| article type
| |
| is part of this journal
| |
