First Local Minimum of the Formic Acid Dimer Exhibits Simultaneously Red-shifted O-H... O and Improper Blue-shifted C-H... O Hydrogen Bonds
1.
SYSNO ASEP
0101111
Druh ASEP
J - Článek v odborném periodiku
Zařazení RIV
J - Článek v odborném periodiku
Poddruh J
Ostatní články
Název
First Local Minimum of the Formic Acid Dimer Exhibits Simultaneously Red-shifted O-H... O and Improper Blue-shifted C-H... O Hydrogen Bonds
Překlad názvu
První lokální minimum dimeru kyseliny mravenčí vykazuje současně vodíkovou vazbu C-H…O s modrým posuvem
Tvůrce(i)
Chocholoušová, Jana (UFCH-W) Špirko, Vladimír (UFCH-W) Hobza, Pavel (UFCH-W)
Zdroj.dok.
Physical Chemistry Chemical Physics. - : Royal Society of Chemistry
- ISSN 1463-9076
Roč. 6, č. 1 (2004), s. 37-41
Poč.str.
5 s.
Jazyk dok.
eng - angličtina
Země vyd.
GB - Velká Británie
Klíč. slova
correlated ab initio ; dimerization ; complexes
Vědní obor RIV
CF - Fyzikální chemie a teoretická chemie
CEP
LN00A032 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy
CEZ
AV0Z4040901 - UFCH-W
Anotace
The first local minimum of the formic acid dimer exhibits simultaneously red-shifted O-H...O and blue-shifted C-H...O hydrogen bonds. The improper, blue-shifted hydrogen bond was investigated by means of the NBO analysis, rehybridization model and optimization in the electric field. It was shown that the electrostatic model cannot describe the nature of the blue-shifted H-bond. From the NBO analysis it becomes evident that the formation of the O-H...O hydrogen bond and C-H...O improper hydrogen bond can be explained on the basis of an increase of electron density in the sigma* antibonding O-H orbital and a decrease of electron density in the sigma* antibonding C-H orbital. While the former effect is easily explained on the basis of hyperconjugation, the latter requires the existence of a new mesomeric structure characterized by delocalization of electron density from the C-H sigma* antibonding orbital to the remaining part of the complex.
