Solvent and structural effects in the N-H bond homolytic dissociation energy

• Type: Article in International Scientific Journal
• Date: 2004

Authors

Gomes, JRB (Author) Other; da Silva, MDMCR (Author) FCUP; da Silva, MAVR (Author) FCUP

Journal

Title: Journal of Physical Chemistry A

Vol. 108

Pages: 2119-2130

ISSN: 1089-5639

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 52 Citations

Scopus - 53 Citations

Scientific classification

FOS: Natural sciences > Chemical sciences

Other information

Authenticus ID: P-000-B70

DOI: 10.1021/jp037996v

Abstract (EN): In this work, the gas-phase homolytic N-H bond dissociation enthalpy (BDE) was investigated for a large series of molecules containing at least one N-H bond by means of accurate density-functional theory calculations. The molecules studied belong to different classes of compounds, namely, amines, amides and anilines, amino acids, phenoxazines, indolamines, and other compounds of general interest, such as anti-inflammatory drugs. To achieve these purposes, the (RO)B3LYP/6-311+G(2d,2p)//(U)B3LYP/6-31G* level of theory was used. The calculated gas-phase N-H BDEs, at T = 298.15 K, are in the range 499.6-203.9 kJ/mol, for purine and HNO, respectively. Further, the calculated BDEs are in excellent agreement with a significant number of available experimental BDEs. Solvent effects were also taken in account, and rather significant differences are found among N-H BDEs computed in the gas phase and in heptane, DMSO, or water.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 12