The interactions between alkali metals and C2H2. Density functional theory as an analytic tool

✍ Scribed by Leif A. Eriksson; Jian Wang; Russell J. Boyd

• Book ID: 103031272
• Publisher: Elsevier Science
• Year: 1995
• Tongue: English
• Weight: 700 KB
• Volume: 235
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(95)00141-p

✦ Synopsis

The interactions between an alkali metal atom (Li, Na, K) and acetylene/vinylidene are investigated by means of gradient corrected ('PWP') density functional theory. Particular emphasis is made on the determination of equilibrium geometries, energetics and atomic hyperfine structures of the M-HCCH van der Waals addition complexes, and the M=HCCH and M-CCH, charge-ffansfer complexes. The PWP optimized geometries are found to be similar to previous ab inilio data, and the generated hyperfine structures are in excellent accord with experimental matrix isolation ESR data recorded at 4 K. In the charge transfer complex formation, the metal atoms are found to donate 0.6-0.8 electron from an excited p orbital to the antibonding CC w" orbital of the hydrocarbon fragment. The calculated trend in charge donation matches the order of increasing atomic s =* p excitation energies, K < Li < Na. This is the first applicalion of the present method to metal atom hyperfine structures, and the resulls are promising for fitlure studies.