By Hofstader R.A., Milner O.I., Runnels J.H. (eds.)
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A more detailed discussion of our results on formic acid chains including the application of larger basis sets will be given elsewhere \117\. 4. Some General Features of Hydrogen Bonding in Infinite Chains Among other properties hydrogen bonds X-H----Y are usually characterized by the following features \55\: i) a smaller H----Y distance than the sum of their van der Waals radii. ii) increase of the X-H bond length. iii) reduction of the X-H stretching frequency. iv) increase of the polarity of the X-H bond accompanied by an increase in dipole moments and dipole moment derivatives.
Formic acid being the first member of the carboxylic acid series seems to be best suited for a theoretical analysis. The isolated formic acid molecule may occur in the syn- and anti- conformation (see figure 5). From extensive micro- H \ / H H \. / C 1/ ~ ,0 0 .......... H, '" "" "" DIMER H 0 \ / '-.... H, ,, C II "0 0 II ~ ~ ( /"""" ......... - ~ ~ 0 CHAIN Figure 5: Syn- and anti- conformations of formic acid, cyclic vapor phase dimer and infinite chain in solid B-formic acid. KARPFEN 46 anti- conformations are well established.
9. Suhai, S. 1980, J. Chern. Phys. 73, 3843. 10. o. 1956, Advan. Phys. 5, I. a. Pisani, C. and Dovesi, R. 1980, Int. J. Quantum Chern. 17, 501. b. , Pisani, C. and Roetti, C. 1980, Int. J. Quantum Chern. 17, 517. a. O'Shea, F. P. 1974, Chern. Phys. Lett. 25, 164. b. 1. 1975, Theoret. Chim. Acta. 38, 139. c. , Demanet, Ch. L. 1978, Chern. Phys. Lett. 54, 186. 13. Delhalle, J. ,to be published. a. G. and Delhalle, J. 1981, Chern. Phys. Lett. 77, 143. b. , Themans, B. and Piela, L. 1983, Int. J. Quantum Chern.