Abstract
By both the EHT and the CNDO/2 calculations, the linear dimer of methanol is found to be more stable than the cyclic dimer. The hydrogen bonds in the trimer are stronger than those in linear dimers. The proton potential function, charge densities, and overlap populations in the linear dimer of methanol have been obtained. The CNDO/2 calculations show that the cis-form of formic acid is more stable than the trans-form, in agreement with experimental data. The cyclic dimer of formic acid is more stable than the open dimer. The β-form of formic acid trimer is more stable than the α-form. The proton potential function and the charge densities in the cyclic dimer of formic acid have been obtained. The CNDO/2 method gives more realistic proton potential functions for the dimers of methanol and formic acid. The O ... O stretching force constant in the dimers of methanol and formic acid have been estimated to be 0.13 × 105 dynes/cm and 0.27 × 105 dynes/cm, respectively, in agreement with experimental data.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Pimentel, G. C., and A. L. McClellan: The hydrogen bond. San Francisco: W. H. Freeman 1960.
Murthy, A. S. N., and C. N. R. Rao: Appl. Spectroscopy Revs. 2, 69 (1968).
Coulson, C. A.: In: Hydrogen bonding. Ed. by D. Hadzi. London: Pergamon Press 1959.
Bratoz, S.: In: Advances in quantum chemistry, Vol. 3. Ed. by P. O. Löwdin. London: Academic Press 1967.
Rein, R., and F. E. Harris: J. chem. Physics 41, 3393 (1964); 42, 2177 (1965); 43, 4415 (1965); 45, 1797 (1966).
Sabin, J. R.: Intern. J. quantum Chem. 2, 23, 31 (1968).
Morokuma, K., H. Kato, T. Yonezawa, and K. Fukui: Bull. chem. Soc. Japan 38, 1263 (1965).
Adam, W., A. Grimison, R. Hoffmann, and C. Z. de Ortiz: J. Amer. chem. Soc. 90, 1509 (1968).
Clarke, G. A., R. Rein, and F. E. Harris: Abstract S 023,155 th National ACS meeting, San Francisco, April 1968.
Hoffmann, R.: J. chem. Physics 39, 1397 (1963).
Pople, J. A., D. P. Santry, and G. A. Segal: J. chem. Physics 43, S 129 (1965); - Pople, J. A., and G. A. Segal: J. chem. Physics 43, S 136 (1965); 44, 3289 (1966).
Davis, J. C., K. S. Pitzer, and C. N. R. Rao: J. physic. Chem. 64, 1714 (1960).
Bellamy, L. J., and R. J. Pace: Spectrochim. Acta 22, 525 (1966).
Jakobsen, R. J., Y. Mikawa, and J. W. Brasch: Spectrochim. Acta 23 A, 2199 (1967).- Mikawa, Y., R. J. Jakobsen, and J. W. Brasch. J. chem. Physics 45, 4750 (1966).
Wolfsberg, M., and L. Helmholz: J. chem. Physics 20, 837 (1952).
Hoffmann, R.: Quantum Chemistry Program Exchange (QCPE 30), Bloomington, Indiana.
Segal, G. A.: Quantum Chemistry Program Exchange (QCPE 91), Bloomington, Indiana.
Kimura, K., and M. Kubo: J. chem. Physics 30, 151 (1959).
Lake, R. F., and H. W. Thompson: Proc. Roy. Soc. (London) A 291, 469 (1966).
Miyazawa, T., and K. S. Pitzer: J. chem. Physics 30, 1076 (1959).
Karle, J., and L. O. Brockway: J. Amer. chem. Soc. 66, 574 (1944).
Waldstein, P., and L. A. Blatz: J. physic. Chem. 71, 2271 (1967).
Stanevich, A. E.: Optics and Spectroscopy 16, 539 (1964).
Ocvirk, A., A. Ažman, and D. Hadži: Theoret. chim. Acta (Berl.) 10, 187 (1968).
Holtzberg, F., B. Post, and I. Fankuchen: Acta crystallogr. 6, 127 (1953).
Pullman, A., and H. Berthod: Theoret. chim. Acta (Berl.) 10, 461 (1968).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Murthy, A.S.N., Davis, R.E. & Rao, C.N.R. Hydrogen bonding: A molecular orbital treatment by the EHT and the CNDO/2 methods of methanol and of formic acid. Theoret. Chim. Acta 13, 81–90 (1969). https://doi.org/10.1007/BF00527322
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00527322